WO2015119414A1 - Accumulateur produisant de l'eau douce - Google Patents

Accumulateur produisant de l'eau douce Download PDF

Info

Publication number
WO2015119414A1
WO2015119414A1 PCT/KR2015/001106 KR2015001106W WO2015119414A1 WO 2015119414 A1 WO2015119414 A1 WO 2015119414A1 KR 2015001106 W KR2015001106 W KR 2015001106W WO 2015119414 A1 WO2015119414 A1 WO 2015119414A1
Authority
WO
WIPO (PCT)
Prior art keywords
secondary battery
sodium
negative electrode
positive electrode
combination
Prior art date
Application number
PCT/KR2015/001106
Other languages
English (en)
Korean (ko)
Inventor
김영식
박정선
정무영
Original Assignee
국립대학법인 울산과학기술대학교 산학협력단
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020150009386A external-priority patent/KR20150091984A/ko
Application filed by 국립대학법인 울산과학기술대학교 산학협력단 filed Critical 국립대학법인 울산과학기술대학교 산학협력단
Priority to JP2016549730A priority Critical patent/JP2017510937A/ja
Publication of WO2015119414A1 publication Critical patent/WO2015119414A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/4604—Treatment of water, waste water, or sewage by electrochemical methods for desalination of seawater or brackish water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/38—Construction or manufacture
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46133—Electrodes characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/46—Apparatus for electrochemical processes
    • C02F2201/461—Electrolysis apparatus
    • C02F2201/46105—Details relating to the electrolytic devices
    • C02F2201/46195—Cells containing solid electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a secondary battery capable of layer discharge. More specifically, the present invention relates to a secondary battery capable of producing fresh water in a layer discharge process. [Technique to become background of invention]
  • a secondary battery means a battery that can be charged and discharged by converting between chemical energy and electrical energy by using a material capable of electrochemical reaction at the positive electrode and the negative electrode.
  • a typical example of such a battery is a lithium secondary battery that generates electrical energy by a change in the chemical potential (chemi cal potent al) when lithium ions are intercalated / deintercalated at a positive electrode and a negative electrode.
  • the lithium secondary is manufactured by using a material capable of reversible intercalation / deintercalation of lithium ions as a positive electrode and a negative electrode active material, and filling an organic electrolyte or a polymer electrolyte between the positive electrode and the negative electrode.
  • lithium is present in a limited amount on the earth and is generally obtained through a difficult process from minerals, salt lakes and the like. Accordingly, there is a problem in that high cost and high energy are used for manufacturing a battery, and a situation in which a next generation secondary battery capable of replacing lithium is required.
  • Desalination technology is used for evaporation, reverse osmosis, electrodialysis, forward osmosis, etc., and research is being conducted to minimize the use of energy required for desalination.
  • the secondary battery and the desalination apparatus are separately developed and installed separately, the secondary batteries and the desalination apparatuses are required to be developed in order to integrate and operate them in one apparatus.
  • seawater is used, and a freshwater producing secondary battery capable of producing freshwater from seawater is provided. [Solution of problem]
  • a secondary battery includes a positive electrode unit including a sodium-containing solution and a positive electrode current collector impregnated in the sodium-containing solution; A negative electrode portion comprising a liquid organic electrolyte and a negative electrode electrode impregnated in the liquid organic electrolyte and having a negative electrode active material charge on the surface thereof; A solid electrolyte positioned between the anode portion and the cathode portion; And a fresh water discharge part connected to the anode part to draw out fresh water generated from the anode part to the outside during layer formation.
  • the fresh water discharge part may include a discharge pipe connected to the positive electrode part containing the sodium-containing solution and selectively opened and closed to discharge fresh water.
  • the anode portion may further include an inlet portion connected to one side and an outlet portion for supplying a sodium-containing solution to the anode portion and / or an outlet portion for discharging the sodium-containing solution at the anode portion.
  • the cathode terminal may further include a cathode terminal electrically connected to the cathode current collector. It may further include a negative electrode terminal electrically connected to the negative electrode.
  • the organic electrolyte in the negative electrode portion may include a non-aqueous organic solvent and / or sodium salt.
  • the non-aqueous organic solvent may be a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, aprotic solvent, or a combination thereof.
  • the sodium salt is NaC10 4 , NaPF 4 , NaPF 5 , NaAsF 6) NaTFSI, Na Bet i (NaN [S0 2 C 2 F 5 ] 2 ), NaCF 3 S0 5 . Or combinations thereof.
  • the negative electrode active material layer formed on the negative electrode includes a negative electrode active material, a conductive material, and / or a binder, the negative electrode active material is a carbon-based material, sodium alloy material, sodium intercalation, and / or It may include a composite material of a combination thereof.
  • the negative active material may include all electrode materials having a potential of less than 4.07 V vs Na / Na + .
  • the carbonaceous material may be natural graphite, artificial graphite, soft carbon, hard carbon, or a combination thereof.
  • the sodium alloy material may be Si, Sn, Bi, Si0 2 , Sb 2 0 4) Si / C, Sb / C composite (compos i te), SnSb / C composite (compos i te), amorphous (amorphous) ) P / C Composites, or combinations thereof.
  • the sodium intercalation material is Li 4 Ti 5 0 12 , NaCo 2 0 4) Na 2 Ti 3 0 7 , Fe 3 0 4 , Ti0 2 , TiS 2 , VS 2 , Sb 2 0 4 ( Sb / C composite ( composite, SnSb / C composite, amorphous P / C composite, or a combination thereof.
  • the electrode material having a potential of less than 4.07 V vs Na / Na + is Na 2 FeP0 4 F, NaFeP0 4 (
  • the conductive material may be a natural alum, artificial alum, carbon black, acetylene black, ketjen black, or a carbon-based material such as carbon fiber; Metal powders that are copper, nickel, aluminum, or silver; Metal fibers; Conductive polymers; Or a combination thereof.
  • the binder is polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, carboxylated polyvinyl chloride polyvinyl fluoride, polymer containing ethylene oxide, polyvinylpyridone, polyurethane, Polytetrafluoroethylene, polyvinylidene fluoride, polyethylene polypropylene, styrene-butadiene rubber, acrylated styrene-butadiene rubber, epoxy resin, nylon, or combinations thereof.
  • the solid electrolyte is beta-alumina ( ⁇ - ⁇ 1 2 0 3 ), amorphous ionic conductivity material (phosphorus-based glass, oxide one based glass, oxide / sulfide based glass), Nasicon (Na super ionic conductor, NASI CON ), Sodium sulfide-based solid electrolyte, sodium oxide-based solid electrolyte, or a combination thereof.
  • the cathode current collector is a carbon paper. Carbon fiber, carbon cloth, carbon felt, metal thin film, or a combination thereof.
  • the positive electrode current collector may have a structure coated with carbon black such as a vulcan, metal catalyst, metal oxide catalyst, conductive material, graphene oxide, or a combination thereof.
  • the porosity of the positive electrode current collector may be 1 to 250.
  • the secondary battery may be generated at the positive electrode portion of the following reaction formula 1 and / or reaction formula 2 during discharge.
  • the secondary battery may occur at the positive electrode portion of Scheme 3 and / or Scheme 4 during charging.
  • the sodium containing solution may be seawater.
  • a secondary battery can be manufactured at a lower cost by using abundant and easy to obtain resources such as seawater.
  • FIG. 1 is a view schematically showing the principle of a secondary battery according to the present embodiment.
  • FIGS. 2 and 3 are diagrams showing a schematic configuration of a secondary battery according to the present embodiment.
  • FIG 4 and 5 are schematic views for explaining the operation of the secondary battery according to the present embodiment.
  • 6 is a graph showing charge and discharge characteristics of the secondary battery according to the present embodiment.
  • 7 is a graph illustrating cycle characteristics of a rechargeable battery according to the present embodiment.
  • 8 is a graph showing the electrical energy efficiency according to the scanning speed of the secondary battery according to the present embodiment.
  • 9 and 10 are graphs of the concentrations of Na silver and C1 ions after layer charging of the secondary battery according to the present embodiment.
  • 11 and 12 are graphs showing the desalination efficiency according to the scanning speed of the secondary battery according to the present embodiment. [Specific contents to carry out invention]
  • 1 to 5 schematically show a secondary battery according to the present embodiment.
  • this embodiment will be described with reference to FIGS. 1 to 5.
  • the secondary battery 100 of this embodiment is a secondary battery having a structure using seawater as an example of a sodium-containing solution.
  • 1 illustrates a schematic principle of a secondary battery. It can be seen from FIG. 1—that the secondary battery according to the present embodiment is driven by using the potential difference according to the change in the concentration of sodium ions in the sodium-containing solution (eg, seawater).
  • FIGS. 2 and 3 illustrate the internal structure of the secondary battery according to the present embodiment, and a secondary battery briefly manufactured for performing a layer discharge experiment.
  • the secondary battery 100 of this embodiment includes a positive electrode portion 10 including a sodium containing solution and a positive electrode current collector 12 impregnated in the sodium containing solution; A negative electrode portion 20 including a liquid organic electrolyte and a negative electrode 22 impregnated in the liquid organic electrolyte and having a negative electrode active material layer; A solid electrolyte 30 positioned between the anode portion and the cathode portion; And a fresh water discharge part 40 connected to the positive electrode part to draw out fresh water generated from the positive electrode part to the outside by the secondary battery layer charge.
  • reference numeral 60 is a body forming the outline of the secondary battery.
  • the body 60 accommodates an anode part and a cathode part therein and electrically insulates the anode part and the cathode part *.
  • the body 60 may be made of polyethylene material, for example.
  • the body is not particularly limited in form or material thereof.
  • the positive electrode part 10 may include a positive electrode terminal 62 electrically connected to the positive electrode current collector 12 and installed to extend outside the body 60.
  • the positive terminal 62 may be made of, for example, a metal material such as stainless steel.
  • the negative electrode unit may include a negative electrode terminal 64 electrically connected to the negative electrode 22 and installed to extend outside the body.
  • the negative terminal 64 is provided separately from the negative electrode and the negative terminal Can be electrically connected.
  • the negative electrode current collector constituting the negative electrode terminal may be extended to the outside of the body 60 to serve as a negative electrode terminal.
  • the fresh water discharge unit 40 is installed in the positive electrode unit 10 containing the sodium-containing solution is selectively opened and closed after the battery layer charge or charge is completed to discharge the fresh water. . .
  • the negative electrode unit may be replaced with a new structure including the negative electrode active material.
  • Reaction Schemes 1 and / or 2 may occur at the positive electrode portion during discharge.
  • the secondary battery according to the present embodiment may occur at the following reaction formula 3 and / or tetravalent positive electrode portion during layer charging.
  • the layer discharge of the battery can be made from the reaction.
  • Batteries of this structure use sodium as an energy source instead of lithium, which may be the next generation alternative to lithium.
  • layer discharge may be possible using sodium-containing solutions (eg seawater) and human body fluids of similar composition.
  • sodium-containing solutions eg seawater
  • human body fluids of similar composition eg seawater
  • the application is very It can be extended in various ways.
  • One side of the positive electrode 10 may be connected to the inlet 50 of the sodium-containing solution.
  • an outlet for discharging the sodium-containing solution from the anode to the outside may be provided separately from the inlet. It may be possible to continuously supply the sodium-containing solution to the anode portion via the inlet portion 50 and the outlet portion installed in the anode portion 10.
  • the secondary battery 100 is removed by moving sodium to the negative electrode part in the positive electrode part by a semi-formulation occurring in the positive electrode part 10 during layer formation.
  • the sodium-containing solution contained in the anode portion was converted into fresh water.
  • the fresh water in the anode part may be drawn out to the outside by opening the fresh water discharge part 40 connected to the anode part 10 when all the sodium in the anode part is removed and the layer is completed.
  • the fresh water discharge portion 40 may include a discharge pipe 42 is installed at the lower end of the anode portion 10 and selectively opened and closed.
  • the secondary battery may have a structure in which fresh water is drawn out through the outflow part, if necessary, using the outflow part provided to distribute sodium to the positive electrode part as a fresh water discharge part.
  • the secondary battery of the present embodiment can supply electrical energy through layer discharge of the secondary battery and convert seawater into fresh water during charging.
  • the negative electrode unit may include an organic electrolyte.
  • the organic electrolyte in the negative electrode portion may include a non-aqueous organic solvent and / or sodium salt.
  • the non-aqueous organic solvent serves as a medium through which ions involved in the electrochemical reaction of the cell can move.
  • the non-aqueous organic solvent may be a carbonate, ester, ether, ketone, alcohol or aprotic solvent.
  • the carbonate solvent include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), and ethylene carbonate ( EC), propylene carbonate (PC), butylene carbonate (BC) and the like can be used
  • the ester solvent is methyl acetate, ethyl acetate, n-propyl acetate, 1, 1-dimethylethyl acetate, methyl propionate , Ethylpropionate, ⁇ -butyrolactone, decanolide, valerolactone, mevalonol actone, Caprolactone and the like can be used.
  • ether solvent dibutyl ether, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraglyme, diglyme, dimethicane, 2-methyltetrahydrofuran, tetrahydrofuran, etc.
  • ketone solvent cyclonucleanone may be used.
  • ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol solvent, and the aprotic solvent may be R-CN (R is a C 2 to C 2 0 linear, branched or cyclic hydrocarbon.
  • amides such as dioxolane sulfolanes such as 1,3-dioxolane and the like. Can be.
  • the non-aqueous organic solvent may be used alone or in combination of one or more, and the mixing ratio in the case of using one or more in combination can be appropriately adjusted according to the desired battery performance, which is widely understood by those skilled in the art. Can be.
  • the carbonate-based solvent it is preferable to use a mixture of cyclic (cyc l i c) carbonate and chain carbonate.
  • the cyclic carbonate and the chain carbonate may be mixed and used in a volume ratio of about 1: 1 to about 1: 9, so that the performance of the electrolyte may be excellent.
  • the non-aqueous organic solvent may further include the aromatic hydrocarbon organic solvent in the carbonate solvent.
  • the ' carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of about 1: 1 to about 30: 1.
  • the aromatic hydrocarbon-based organic solvent of the following Chemical Formula 4 may be used.
  • R 6 are each independently hydrogen, halogen, C1 to An alkyl group of CIO, a haloalkyl group of CI to CIO, or a combination thereof.
  • the aromatic hydrocarbon organic solvent is benzene, fluorobenzene,
  • 1.4-difluoroluene, 1,2,3-trifluoroluene, 1,2,4 ⁇ trifluoroluene, chloroluene, 1,2-dichloroluene, 1,3-dichloro Luene, 1,4-dichloroluene, 1,2,3-trichloroluene, 1,2,4-trichloroluene, iodoluene, 1,2-diaioluluene, 1,3- Diiodoluene, 1,4-Diiodoluene, 1,2,3-triiodoluene, 1,2,4 ⁇ triiodoluene, xylene or a combination thereof may be used.
  • the non-aqueous electrolyte may further include vinylene carbonate or an ethylene carbonate compound of Formula 5 to improve battery life.
  • R 7 and R 8 are each independently hydrogen, a halogen group, a cyano group (CN), a nitro group (N0 2 ) or a fluoroalkyl group of C1 to C5, and at least one of R 7 and R 8 Is a halogen group, cyano group (CN), nitro group (N0 2 ) or a C1 to C5 fluoroalkyl group.
  • Representative examples of the ethylene carbonate-based compound include difluoro ethylene carbonate, chloroethylene carbonate, dichloroethylene carbonate, bromoethylene carbonate, dibromoethylene carbonate, nitroethylene carbonate cyanoethylene carbonate, fluoroethylene carbonate, and the like. Can be mentioned.
  • the amount of vinylene carbonate or the ethylene carbonate-based compound may be appropriately adjusted to improve the life.
  • the sodium salt may be NaC10 4 , NaPF 4 , NaPF 6 , NaAsF 6 , NaTFSI, Na Beti (NaN [S0 2 C 2 F 5 ] 2 ), NaCF 3 SO 5 or a combination thereof.
  • the concentration of the sodium salt may be from 0.001 to 10M, more specifically, may be in the range of 0.1 to 2.0M.
  • concentration of the sodium salt is included in the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and sodium ions can move effectively.
  • the negative electrode active material layer positioned on the surface of the negative electrode may include a negative electrode active material, a conductive material, and / or a binder.
  • the anode active material may include a composite material which is a carbonaceous material, a sodium alloy material, a sodium intercalation, and / or a combination thereof.
  • the negative active material may include all electrode materials having a potential of less than 4.07 V vs Na / Na + .
  • the carbonaceous material may be natural graphite, artificial graphite, soft carbon, hard carbon, or a combination thereof. More specifically, it may be a hard carbon.
  • the sodium alloy material may be Si, Sn, Bi, Si0 2 , Sb 2 0 4 , Si / C, Sb / C composite, SnSb / C composite, amorphous P / C complex, or a combination thereof.
  • the sodium intercalation material is Li 4 Ti 5 0 12 , NaCo 2 0 4 ( Na 2 Ti 3 0 7 , Fe 3 0 4 , Ti0 2 , Ti3 ⁇ 4, VS 2 , Sb 2 0 4 , Sb / C composite (composite ), A SnSb / C composite, an amorphous P / C composite, or a combination thereof, and more specifically, the sodium intercalation material may be Li 4 Ti 5 0 12 . .
  • the electrode material having a potential lower than 4.07 V vs Na / Na + is Na 2 FeP0 4 F, NaFeP0 4 , BP0E, ⁇ HFC, Na 3 V (P0 4 ) 3 / C, ⁇ 3 ⁇ .5 ⁇ 0 4 . 8 ⁇ 0 . 7 or a combination thereof.
  • the negative electrode active material layer also includes a binder, and may optionally further include a conductive material.
  • the binder adheres the negative electrode active material particles to each other well, and also adheres the negative electrode active material to the current collector, and representative examples thereof include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl chloride, and carbon.
  • Polyvinylchloride, polyvinylfluoride, polymers containing ethylene oxide, polyvinylpyridone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber Acrylated styrene-butadiene rubber, epoxy resin, nylon, etc. may be used, but is not limited thereto.
  • the conductive material is used to impart conductivity to the electrode. Any conductive material may be used as long as it does not cause chemical change in the battery to be constructed. Examples thereof include natural alum, artificial alum, carbon black, acetylene black, and ketjen black. Carbon-based materials such as carbon fiber; Metal materials such as metal powder or metal fibers such as copper, nickel, aluminum and silver; Conductive polymers such as polyphenylene derivatives; Or a conductive material containing a mixture thereof.
  • copper foil nickel foil, stainless steel foil, titanium foil, nickel foam, copper foam, a polymer substrate coated with a conductive metal, or a combination thereof may be used.
  • the negative electrode is prepared by mixing an active material, a binder, and a conductive material in a solvent to prepare an active material composition, and applying the composition to a current collector to produce a negative electrode. Since such an electrode manufacturing method is well known in the art, detailed description thereof will be omitted.
  • the solvent ⁇ may be N-methylpyridone and the like, but is not limited thereto.
  • the solid electrolyte is a material that can be the moving speed of the sodium ion stability and fast solution and the organic solution, the beta-alumina ( ⁇ - ⁇ 1 2 3 ⁇ 4), amorphous ionic conductivity material (phosphorus-based gl ass, oxide-based glass, oxide / sulfide-based glass, Na super ion conductor (NASI CON), sodium sulfide-based solid electrolyte, sodium oxide-based solid electrolyte, or a combination thereof.
  • the beta-alumina ⁇ - ⁇ 1 2 3 ⁇ 4
  • amorphous ionic conductivity material phosphorus-based gl ass, oxide-based glass, oxide / sulfide-based glass, Na super ion conductor (NASI CON)
  • sodium sulfide-based solid electrolyte sodium oxide-based solid electrolyte, or a combination thereof.
  • the solid electrolyte may be nasicon, in which case the ionic conductivity may be further improved.
  • the positive electrode current collector included in the positive electrode portion may be carbon paper, carbon fiber, carbon cloth, carbon felt, metal thin film, or a combination thereof, and more specifically, may be carbon paper. In the case of carbon paper, it is possible to minimize the by-products resulting from the oxidation / reduction reaction of other metal ions contained in the sodium-containing solution.
  • the positive electrode current collector may have a structure coated with carbon black such as a vulcan, metal catalyst, metal oxide catalyst, conductive material, graphene oxide, or a combination thereof.
  • the porosity of the positive electrode current collector may range from 1 to 250 m . When satisfying such a range, more electrode reactions can be induced by constructing an electrode having a large surface area. Examples and comparative examples of the present invention are described below. The following examples are merely examples of the present invention and the present invention is not limited to the following examples.
  • Carbon paper (Fuel Cel l Store, 2050-A) was used as the positive electrode current collector. After adding the seawater in the positive electrode container, the positive electrode current collector was impregnated with seawater to prepare a positive electrode.
  • the voids of the carbon paper are 28 / m.
  • Stainless steel (McMASTER) was used as the current collector.
  • An electrode was prepared.
  • the organic electrolyte was prepared by mixing ethylene carbonate (EC): diethylene carbonate (DEC) (1: 1vol ratio) and 1M NaC10 4 sodium salt (Aldr i ch).
  • NASICON Na 3 Zr 2 Si 2 P0 12
  • the solid electrolyte was made through a solid id-state react ion in the laboratory. Solid phase reactions well known in the art will be omitted for specific methods.
  • a solid electrolyte was placed between the positive electrode and the negative electrode.
  • the thickness of the solid electrolyte is 1 mm.
  • An inlet and an outlet for supplying a sodium-containing solution were installed on the side and bottom of the vessel forming the anode, and the outlet installed at the bottom of the vessel was used as a freshwater discharge portion for discharging fresh water.
  • 6 is a graph showing the layer discharge characteristics of the secondary battery according to the present embodiment. 6 shows that sodium ions dissolved in seawater accumulate in the hard carbon in the negative electrode by layering the seawater battery in this embodiment. Accumulated sodium ions are discharged back into the sea water, producing electricity when the battery is discharged. The layer voltage is about 3V on average, and the discharge voltage is about 2.3V on average. In the first cycle, an irreversible capacity of about 31% was observed, which represents the amount of sodium ions consumed in the formation of the solid electrolyte interface (SEI) that forms on the surface of the cathode when it first enters the cathode. After SEI formation, it shows stable reversible capacity. Cycle characteristic evaluation
  • FIG. 7 is a graph illustrating cycle characteristics of a rechargeable battery according to the present embodiment. As shown in FIG. 7, the present example shows a stable reversible capacity after SEI formation in the first cycle, and shows an effect of 84% even after about 40 cycles.
  • FIG. 8 is a graph showing the electrical energy efficiency according to the scanning speed in the secondary battery according to the present embodiment.
  • a "voltage, increase the scanning speed to 0.1mA, 0.2mA was measured at 0.05mA. As shown in FIG. 8, it can be seen that at 0.05 mA, the voltage is 3.98 V, and when the scanning speed is increased to 0.1 mA and 0.2 mA, the voltage increases to 4.32 V and 4.54 V, respectively.
  • the electrical energy required to layer the secondary battery of this embodiment is 0.199mW, 0.432mW, 0.0908mW at 0.05mA, 0.1mA, 0.2mA, respectively.
  • 9 and 10 charge the secondary battery of this example in units of 10 hours up to 50 hours at a scanning speed of 0.2 mA, and then measure the concentrations of Na ions and C1 ions using ion chromatography.
  • points represent measured values and straight lines represent correction values through linear fitting.
  • 9 shows the value obtained by measuring Na ion concentration. 9, it can be seen that when the secondary battery of the present embodiment is layered, the Na ion concentration decreases by about 830 ppm. 10 has shown the value which measured the density
  • 11 and 12 show the desalination efficiency according to the scanning speed of the secondary battery of this embodiment. Concentrations were measured in units of 10 hours for 50 hours while increasing the scanning speed from 0.05 mA to 0.1 and 0.2 mA. 11 and 12 are graphs measuring Na ion concentration and CI ion concentration using IC respectively. 11 and 12 are shown after linear fitting.
  • the absolute value of the tilt device of 0.05 mA was 11.94 and the absolute value of the slope increased to 16.00 and 16.63 as the scan rate was increased to 0.1 and 0.2 mA.
  • the absolute value of the slope is 18.51 at the scan rate of 0.05 mA and the scan rate is 0.
  • the value increased to 1, 0.2mA the absolute value of the gradient increased to 36.00 and 45.29, respectively. From this, it was confirmed that the desalination efficiency can be increased by increasing the scanning speed and injecting large electric energy.
  • the present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person having ordinary knowledge in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention porte sur un accumulateur et un système d'accumulateurs, et concerne un accumulateur produisant de l'eau douce, comprenant : une unité d'électrode positive incluant une solution contenant du sodium et un collecteur de courant d'électrode positive imprégné dans la solution contenant du sodium ; une unité d'électrode négative incluant un électrolyte organique liquide et une électrode négative imprégnée dans l'électrolyte organique liquide et comportant une couche de matériau actif d'électrode négative ; un électrolyte solide positionné entre l'unité d'électrode positive et l'unité d'électrode négative ; et une unité de décharge d'eau douce connectée à l'unité d'électrode positive afin de décharger, à l'extérieur, l'eau douce générée par l'unité d'électrode positive pendant la charge.
PCT/KR2015/001106 2014-02-04 2015-02-03 Accumulateur produisant de l'eau douce WO2015119414A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2016549730A JP2017510937A (ja) 2014-02-04 2015-02-03 淡水生産二次電池

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2014-0012555 2014-02-04
KR20140012555 2014-02-04
KR10-2015-0009386 2015-01-20
KR1020150009386A KR20150091984A (ko) 2014-02-04 2015-01-20 담수 생산 이차전지

Publications (1)

Publication Number Publication Date
WO2015119414A1 true WO2015119414A1 (fr) 2015-08-13

Family

ID=53778171

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/001106 WO2015119414A1 (fr) 2014-02-04 2015-02-03 Accumulateur produisant de l'eau douce

Country Status (1)

Country Link
WO (1) WO2015119414A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018524758A (ja) * 2016-06-03 2018-08-30 ユニスト（ウルサン ナショナル インスティテュート オブ サイエンス アンド テクノロジー） 二次電池モジュールおよび二次電池モジュールの製造方法
KR20200133053A (ko) * 2019-05-15 2020-11-26 울산과학기술원 담수 생산을 위한 이차 전지 및 이를 포함하는 담수화 장치

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007517979A (ja) * 2003-12-11 2007-07-05 アメリカン パシフィック コーポレイション イオン伝導性セラミックの固体膜を用いたアルカリアルコラートを生成するための電気分解による方法
WO2009011841A1 (fr) * 2007-07-13 2009-01-22 Ceramatec, Inc. Générateur et distributeur d'agent de nettoyage
KR20120062799A (ko) * 2009-08-20 2012-06-14 제너럴 일렉트릭 캄파니 고체 전해질 생산 어셈블리 및 방법
KR101190610B1 (ko) * 2012-04-13 2012-10-15 한국기계연구원 정삼투-연료전지 하이브리드 담수화 및 발전방법 및 이를 이용한 정삼투-연료전지 하이브리드 담수화 및 발전시스템
WO2013134114A2 (fr) * 2012-03-04 2013-09-12 Indiana University Research And Technology Center Procédé et appareil pour l'extraction d'énergie et de métal à partir d'électrodes à eau de mer

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007517979A (ja) * 2003-12-11 2007-07-05 アメリカン パシフィック コーポレイション イオン伝導性セラミックの固体膜を用いたアルカリアルコラートを生成するための電気分解による方法
WO2009011841A1 (fr) * 2007-07-13 2009-01-22 Ceramatec, Inc. Générateur et distributeur d'agent de nettoyage
KR20120062799A (ko) * 2009-08-20 2012-06-14 제너럴 일렉트릭 캄파니 고체 전해질 생산 어셈블리 및 방법
WO2013134114A2 (fr) * 2012-03-04 2013-09-12 Indiana University Research And Technology Center Procédé et appareil pour l'extraction d'énergie et de métal à partir d'électrodes à eau de mer
KR101190610B1 (ko) * 2012-04-13 2012-10-15 한국기계연구원 정삼투-연료전지 하이브리드 담수화 및 발전방법 및 이를 이용한 정삼투-연료전지 하이브리드 담수화 및 발전시스템

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018524758A (ja) * 2016-06-03 2018-08-30 ユニスト（ウルサン ナショナル インスティテュート オブ サイエンス アンド テクノロジー） 二次電池モジュールおよび二次電池モジュールの製造方法
US10573928B2 (en) 2016-06-03 2020-02-25 Unist (Ulsan National Institute Of Science And Technology) Rechargeable battery module and method for manufacturing the same
KR20200133053A (ko) * 2019-05-15 2020-11-26 울산과학기술원 담수 생산을 위한 이차 전지 및 이를 포함하는 담수화 장치
KR102240030B1 (ko) * 2019-05-15 2021-04-14 울산과학기술원 담수 생산을 위한 이차 전지 및 이를 포함하는 담수화 장치

Similar Documents

Publication Publication Date Title
US10992002B2 (en) Secondary battery
KR20150091984A (ko) 담수 생산 이차전지
Walter et al. Challenges and benefits of post-lithium-ion batteries
Wan et al. Energy storage chemistry in aqueous zinc metal batteries
KR20150091834A (ko) 이산화탄소 포집 이차전지
Zhang et al. Assembly of aqueous rechargeable magnesium ions battery capacitor: the nanowire Mg-OMS-2/graphene as cathode and activated carbon as anode
KR20160121998A (ko) 이차 전지 및 파우치형 이차 전지
KR101788180B1 (ko) 염소 또는 염소계 활성물질을 생산하는 이차전지, 이를 이용한 선박 평형수 처리 장치 및 처리 방법
CN102763254B (zh) 高能量密度氧化还原液流装置
JP5099299B2 (ja) リチウム二次電池用正極材料及びその製造方法並びにリチウム二次電池
WO2016114141A1 (fr) Solution électrolytique aqueuse pour dispositif d'accumulation électrique, et dispositif d'accumulation électrique comprenant ladite solution électrolytique aqueuse
TWI633697B (zh) 鈉離子二次電池用正極材料
CN108242560A (zh) 锌基双离子电池及其制备方法
KR20160136703A (ko) 통합 전지 시스템
WO2014121276A2 (fr) Électrodes en sulfure métallique et dispositifs de stockage d'énergie de ces électrodes
Idrees et al. 3D printed PC/SiOC@ Zn hybrid composite as dendrite-free anode for Zn-Ion battery
KR20080091883A (ko) 고용량 리튬 이차전지용 전극 및 이를 함유하는 리튬이차전지
TW201826592A (zh) 用於電池之陽極、陰極及隔板，以及其製造和使用方法
CN108172895A (zh) 二次电池
WO2010124172A2 (fr) Système de batterie métal-air
JP2020024819A (ja) 水系亜鉛イオン電池用正極活物質
KR20180003813A (ko) 나트륨 함유 용액을 이용한 이차전지 및 피부부착형 이차전지
JP2014044820A (ja) リチウム空気電池
Li et al. Reversible transformation of a zinc salt-boosted high areal capacity manganese dioxide cathode for energy-dense and stable aqueous zinc batteries
Ge et al. Towards thermally stable high performance lithium-ion batteries: the combination of a phosphonium cation ionic liquid and a 3D porous molybdenum disulfide/graphene electrode

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15745851

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2016549730

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15745851

Country of ref document: EP

Kind code of ref document: A1