WO2014092493A2 - Batterie secondaire au sodium - Google Patents

Batterie secondaire au sodium Download PDF

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WO2014092493A2
WO2014092493A2 PCT/KR2013/011568 KR2013011568W WO2014092493A2 WO 2014092493 A2 WO2014092493 A2 WO 2014092493A2 KR 2013011568 W KR2013011568 W KR 2013011568W WO 2014092493 A2 WO2014092493 A2 WO 2014092493A2
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Prior art keywords
sodium
bis
secondary battery
butyl
ethyl
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PCT/KR2013/011568
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English (en)
Korean (ko)
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WO2014092493A3 (fr
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채제현
김정수
고원상
이승옥
김영솔
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에스케이이노베이션 주식회사
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Priority claimed from KR1020130153901A external-priority patent/KR102143461B1/ko
Application filed by 에스케이이노베이션 주식회사 filed Critical 에스케이이노베이션 주식회사
Publication of WO2014092493A2 publication Critical patent/WO2014092493A2/fr
Publication of WO2014092493A3 publication Critical patent/WO2014092493A3/fr

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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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

Definitions

  • the present invention relates to a sodium secondary battery, and more particularly, to a sodium secondary battery in which charge / discharge cycle characteristics are stably maintained for a long time, deterioration is prevented, and thus battery life is improved, and battery stability is improved.
  • sodium-based secondary cells such as sodium-sulfur cells or sodium-nickel chloride cells
  • sodium-sulfur batteries should operate at least 250 ° C in the case of sodium-nickel chloride cells, taking into account the conductivity and melting of the cell components.
  • Sodium-sulfur batteries have the disadvantage of having an operating temperature of at least 300 ° C or higher. Due to these problems, there are many disadvantages in terms of manufacturing or operation economics in order to reinforce the temperature maintenance, airtightness maintenance and safety aspects. In order to solve the above problems, room temperature-based sodium-based batteries have been developed, but the output is very low compared to the nickel-hydrogen battery or lithium battery is very low.
  • the positive electrode, the negative electrode and the positive electrode impregnated in the anolyte including a plating additive selected from at least one selected from a negative electrode containing sodium, a suppressor, a leveler, and an accelerator.
  • a plating additive selected from at least one selected from a negative electrode containing sodium, a suppressor, a leveler, and an accelerator.
  • Sodium ion conductive solid electrolyte separating the liquid.
  • the accelerator may be a sulfur-containing organic compound.
  • the accelerator is N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, N, N-dimethyl-dithiocarbamic acid- (3- Sulfoethyl) ester, 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulphonic acid sodium salt, 3-mercapto-propylsulfonic acid- (3-sulfopropyl) ester, 3-mercapto-propylsul Sodium phosphate salt (3-mercaptopropane-1-sulfonic acid sodium salt), 3-mercapto-1-propane sulfonic acid, O-ethyl-dithiocarboxylic acid-S- ( ⁇ -sulfopropyl) -ester, potassium salt Thioglycolic acid, bissulfopropyl disulfide, 3- (benzthiazolyl-s
  • the inhibitor may be an oxygen-containing chain polymer.
  • the inhibitor is carboxymethyl cellulose, nonylphenol polyglycol ether, octanediolbis- (polyalkylene glycol ether), octanol polyalkylene glycol ether, polyethylene glycol ether, Oleic acid polyglycol ester, polyethylene propylene glycol, polyethylene glycol, polyethylene glycol dimethyl ether, polyoxypropylene glycol, polypropylene glycol, polyvinyl alcohol, stearic acid polyglycol ester, stearyl alcohol polyglycol ether, ⁇ -naphthol-polyethylene glycol ether And ethylene oxide-propylene oxide copolymer and butyl alcohol-ethylene oxide-propylene oxide copolymer.
  • the planarizer may be a nitrogen-containing organic material.
  • the planarizing agent is polyimine, organic sulfonate, tertiary amine compound, quaternary amine compound, alkyl ammonium chloride of C4-C35, phenazine dye, phenazine azo Dyes or mixtures thereof.
  • the planarizing agent is 1- (2-hydroxyethyl) -2-imidazolidineethion (HIT), 4-mercaptopyridine, 2-mercaptopyridine , 2-mercaptothiazoline, benzotriazole, benzothiazole, benzimidazole, 0-aminophenol, 2,1,3-benzothiaziazole, phenylenediamine, 2-mercaptobenzothiazole, ethylene thio Urea, thiourea, thiadiazole, imidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2,4-dimethylimidazole , 1-ethylimidazole, 1-ethyl-2-methylimidazole, 1-oxymethylimidazole, 1-vinylimidazole, monoethanolamine, diethanolamine, triethanolamine, dimethylamine, ethylenediamine
  • the anolyte may contain a plating additive of 1.5 ⁇ M to 150 mM molar concentration.
  • the anolyte may contain an accelerator.
  • the anolyte may further contain an inhibitor, and the molar ratio of the accelerator to the inhibitor may be 1: 0.01-2.
  • the anolyte may further contain a flattening agent, and the molar ratio of the accelerator to the flattening agent may be 1: 0.01-2.
  • the secondary battery is charged by the following Scheme 1 and discharged by the following Scheme 2, during the charging and discharging of the battery sodium of Scheme 1 and Scheme 2
  • the halide and the cathode active metal halide may be in a liquid state dissolved in the anolyte.
  • M is a metal selected from at least one of transition metals and group 12-14 metals
  • X is a halogen element
  • m is a natural number of 1 to 4.
  • the sodium secondary battery according to the present invention may have stable charge and discharge cycle characteristics as it contains a plating additive selected from at least one of an accelerator, an inhibitor, and a planarizer.
  • a plating additive selected from at least one of an accelerator, an inhibitor, and a planarizer.
  • FIG. 1 is a cross-sectional view illustrating a structure of a sodium secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a view showing charge and discharge cycle characteristics of a sodium secondary battery according to an embodiment of the present invention
  • FIG. 3 is a view showing charge and discharge characteristics of a sodium secondary battery according to an embodiment of the present invention.
  • a sodium secondary battery according to an embodiment of the present invention is a positive electrode impregnated in the positive electrode solution containing a plating additive selected from at least one of a cathode containing sodium, a suppressor, a leveler, and an accelerator. And a sodium ion conductive solid electrolyte separating the cathode and the anolyte.
  • a sodium secondary battery is a sodium ion conductive solid electrolyte separating a negative electrode space and a positive electrode space, a negative electrode containing sodium in the negative electrode space, an anolyte and an anolyte positioned in the positive electrode space. Impregnated anodes.
  • the anolyte may contain a plating additive selected from at least one of an inhibitor, a flattener, and an accelerator.
  • the plating additive contained in the anolyte may include plating additives used in the conventional plating field for forming a metal film on an object to be plated through an electrolytic or electroless process, and may include an inhibitor, a flatter (leveler), and an accelerator.
  • Glosses can be inhibitors, planarizers and accelerators known to be used in plating baths for plating in the plating art.
  • the plating additives may be inhibitors, planarizers and accelerators used in the plating bath in the electrolytic plating of transition metals and metals of at least one selected from the Group 12-14 metal group.
  • the transition metal includes titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu), 12 to Group 14 metals may include zinc (Zn), aluminum (Al), cadmium (Cd), and tin (Sn).
  • the accelerator has a relatively small size compared to the inhibitor, and is mainly distributed in a narrow space such as pores to reduce metal ions to metal, that is, discharge process of the battery.
  • a narrow space such as pores to reduce metal ions to metal, that is, discharge process of the battery.
  • the inhibitor prevents the reduction of metal ions by surface adsorption, that is, by adsorbing on the surface of the current collector and slowing the electrodeposition rate of the surface, which is likely to cause metal electrodeposition, the metal can be more uniformly deposited.
  • the leveling agent is similar to the inhibitor, but it is mainly adsorbed at the edge of the pore inlet to prevent the inlet from being blocked, thereby allowing the metal to be continuously deposited in the inner space and lowering the surface roughness, that is, the positive electrode current collector. It may serve to reduce the surface roughness of the metal (film) reduced (electrodeposited) to the surface.
  • the anolyte preferably contains at least an accelerator, more preferably, may contain an accelerator and an inhibitor, or may contain both an accelerator, an inhibitor, and a leveling agent.
  • the accelerator may be a sulfur-containing organic compound.
  • it may be a sulfur-containing organic compound having a molecular weight of 1000 g / mol or less, more specifically, a molecular weight of 10 to 1000 g / mol and containing one or more sulfur.
  • the sulfur-containing organic compound may include a sulfur-based organic compound including a sulfur-containing group, and the sulfur-containing group may be a group selected from one or two or more selected from thiol group (mercapto group), sulfonic acid group, sulfinic acid group and thiosulfate group. have. At this time, the sulfur-containing organic compound may not contain nitrogen.
  • the sulfur-containing organic compound may be a material belonging to the general formula R'-SR-SO 3 -X.
  • R is optionally substituted alkyl, optionally substituted heteroalkyl (including cycloalkyl), optionally substituted aryl or optionally substituted heteroalicyclic
  • X is hydrogen, sodium or potassium
  • R ' is hydrogen or chemical Binding (ie, -SR-SO 3 ).
  • alkyl may be C1-C16, specifically C1-C12, more specifically C1-C8.
  • Heteroalkyl may have one or more hetero (N, O or S) atoms in the chain and may be C1-C16, specifically C1-C12, more specifically C1-C8.
  • Aryl can be carbocyclic aryl, for example, phenyl or naphthyl.
  • Heteroaromatics may also belong to aryl and include from 1 to 3 N, O or S; And 1-3 separated or fused rings.
  • the heteroaromatics are comarinil, quinolinyl, pyridyl, pyrazinyl, pyrimidyl, furyl, pyrrolyl, thienyl, thiazolyl, oxazolyl, oxydizolyl, triazole, imidazolyl, indolyl , Benzofuranyl or benzothiazole and the like.
  • Heteroalicyclics comprise 1 to 3 N, O or S; And 1-3 separated or fused rings; for example, tetrahydrofuranyl, thienyl, tetrahydropyranyl, piperidinyl, morpholino or pyrrolidinyl, and the like.
  • Optionally substituted may mean substituted or unsubstituted, and the substituents substituted are, independently of one another, C1-C8 alkoxy; C1-C8 alkyl; Halogen selected from one or more of F, Cl and Br; Cyano; Or nitro or the like.
  • the accelerator may be one or two or more selected from the general formula HO 3 SR 0 -SH, HO 3 SR 1 -SSR 1 -SO 3 H and HO 3 SR 2 -SSR 2 -SO 3 H.
  • R 0 can be an optionally substituted alkyl, specifically, C 1 -C 6, more specifically C 1 -C 4 alkyl.
  • R 1 may be independently substituted alkyl independently of one another, and specifically, may be C1-C6, more specifically C1-C4 alkyl.
  • R 2 may be optionally substituted aryl, and specifically may be optionally substituted phenyl or naphthyl.
  • R 0 Optionally substituted at R 1 or R 2 may mean substituted or unsubstituted, and the substituted substituent is C 1 -C 8 alkoxy; C1-C8 alkyl; Or halogen selected from one or more of F, Cl, and Br.
  • the accelerator is N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester, N, N-dimethyl-dithiocarbamic acid- (3- Sulfoethyl) ester, 3-N, N-dimethylaminodithiocarbamoyl-1-propanesulphonic acid sodium salt, 3-mercapto-propylsulfonic acid- (3-sulfopropyl) ester, 3-mercapto-propylsul Sodium phosphate salt (3-mercaptopropane-1-sulfonic acid sodium salt), 3-mercapto-1-propane sulfonic acid, O-ethyl-dithiocarboxylic acid-S- ( ⁇ -sulfopropyl) -ester, potassium salt Thioglycolic acid, bissulfopropyl disulfide, 3- (benzthiazolyl-s
  • the accelerator may be included in the form of an acid which is not a salt of the sodium salt or potassium salt.
  • 3-mercapto-1-propane sulfonic acid may be used as an accelerator instead of 3-mercapto-propylsulfonic acid sodium salt
  • thioglycolic acid may be used as an accelerator instead of potassium salt thioglycolic acid.
  • the inhibitor may be a chain polymer, preferably an oxygen-containing chain polymer.
  • the chain polymer may comprise a polymer by a single monomer or a copolymer by two or more monomers.
  • Mw mass average molecular weight
  • the inhibitor may be a polymer belonging to the general formula R 3 -O- (CZYCZ'Y'O) n R 3 ′.
  • R 3 and R 3 ' are independently of each other H, C1-C20 alkyl or C6-C10 aryl, Z, Y, Z' and Y 'may be independently of each other hydrogen, alkyl, aryl or aralkyl,
  • the alkyl of Z, Y, Z 'or Y' may be methyl, ethyl or propyl, the aryl of Z, Y, Z 'or Y' may be phenyl and the aralkyl of Z, Y, Z 'or Y' May be benzyl,
  • n may be an integer of 3 to 20,000.
  • the inhibitor may be a polymer of a monomer comprising an oxygen-containing group
  • the oxygen-containing group may be a group selected from one or two or more from hydroxy groups and carboxy groups.
  • the monomer including an oxygen-containing group may be C1-C6 alkyl substituted with an oxygen-containing group.
  • the inhibitor is carboxymethyl cellulose, nonylphenol polyglycol ether, octanediolbis- (polyalkylene glycol ether), octanol polyalkylene glycol ether, polyethylene glycol ether, Oleic acid polyglycol ester, polyethylene propylene glycol, polyethylene glycol, polyethylene glycol dimethyl ether, polyoxypropylene glycol, polypropylene glycol, polyvinyl alcohol, stearic acid polyglycol ester, stearyl alcohol polyglycol ether, ⁇ -naphthol-polyethylene glycol ether At least one selected from the group consisting of ethylene oxide-propylene oxide copolymer and butyl alcohol-ethylene oxide-propylene oxide copolymer.
  • the planarizer may be a nitrogen-containing organic compound.
  • the leveling agent may comprise a nitrogen-containing heteroaromatic organic compound.
  • the nitrogen of the nitrogen-containing organic compound may be in an aromatic ring or conjugated with the ring. In this case, when nitrogen is present in the aromatic ring, one to three nitrogens based on the six-membered ring may be present.
  • the nitrogen-containing organic compound may include a nitrogen-containing heteroaromatic organic compound, and the nitrogen of the nitrogen-containing organic compound may be in an aromatic ring or conjugated with the ring. In this case, when nitrogen is present in the aromatic ring, one to three nitrogens based on the six-membered ring may be present.
  • the nitrogen-containing organic compound may be a polyimine, tertiary amine compound, quaternary amine compound, alkyl ammonium chloride of C4-C35, phenazine dye, phenazine azo dye or mixtures thereof.
  • the penazine dye may include safranin and a derivative thereof
  • the phenazine azo dye may include Janus Green B and a derivative thereof.
  • the nitrogen-containing heteroaromatic organic compound is an aromatic six-membered ring selected from the group consisting of benzene, pyridine, pyrazine, benzoquinone and melamine ring, and in or conjugated with an aromatic ring It may be an aromatic organic compound having two or more heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur atoms. At this time, the aromatic organic compound may be substituted with one or more substituents selected from hydroxy, amino, imino, carboxy, mercapto, nitro, C1-C20 alkyl and C1-C20 alkoxy.
  • the polyimine may be an alkyl polyimine, may be an arylated polyethyleneimine (arylated PEI).
  • arylated PEI arylated polyethyleneimine
  • ah relay suited polyethyleneimine has the general formula R 4 -R 5 NR 6 SO 3 - may be a material belonging to.
  • R 4 is bonded to the C1-C4 alkyl, an aromatic hydrocarbon, sulfonyl, phosphine sulfonyl, an aldehyde or a carbamide
  • R 5 is a pyridine
  • R 6 is C1-C4 alkyl, cycloalkyl, aromatic hydrocarbon ring or R 6
  • hydrogen it may be C 1 -C 4 alkyl, substituted cycloalkyl or substituted aromatic hydrocarbon substituted with any substituent of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.
  • the tertiary amine compound may include an imidazole compound, an aliphatic amine compound or a mixture thereof, and the quaternary amine compound may be formed of a tertiary amine compound and an alkyl halide. May be a reaction product.
  • the imidazole compound is imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole, 1-ethyl-2-methylimidazole and 1-oxymethylimidazole. At least one may be selected from.
  • Aliphatic amine compounds include monoethanolamine, diethanolamine, triethanolamine, dimethylamine, ethylenediamine, diethylenetriamine, iminobispropylamine, triethylenetetramine, tetraethylenepentamine and N, N-bis- It may be one or more selected from (3-aminopropyl) ethylenediamine.
  • halogenated alkyls that react with tertiary amine compounds include monochloroacetic acid, benzylchloride, chloroacetamide, 3-aminobenzylchloride, arylchloride, dichloroethane, monochloropropane, dichloroglycerine or ethylenechlorohydrin, epichloro Hydrin (epichlorohydrine).
  • the flattening agent may be C4-C35 alkyl ammonium chloride, and in detail, may be aliphatic linear trimethylammonium chloride having C8-C18 chain lengths.
  • the planarizing agent is 1- (2-hydroxyethyl) -2-imidazolidineethion (HIT), 4-mercaptopyridine, 2-mercaptopyridine , 2-mercaptothiazoline, benzotriazole, benzothiazole, benzimidazole, 0-aminophenol, 2,1,3-benzothiaziazole, phenylenediamine, 2-mercaptobenzothiazole, ethylene thio Urea, thiourea, thiadiazole, imidazole, 1-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2,4-dimethylimidazole , 1-ethylimidazole, 1-ethyl-2-methylimidazole, 1-oxymethylimidazole, 1-vinylimidazole, monoethanolamine, diethanolamine, triethanolamine, dimethylamine, ethylenediamine
  • the mass average molecular weight may be 10,000 to 200,000, specifically 10,000 to 160,000, and more specifically 10,000 to 70,000.
  • the sodium secondary battery according to an embodiment of the present invention contains a plating additive selected from one or more of the above-described accelerator, inhibitor, and flattener, and thus, metal repeatedly generated at the anode during charging and discharging of the battery.
  • a plating additive selected from one or more of the above-described accelerator, inhibitor, and flattener, and thus, metal repeatedly generated at the anode during charging and discharging of the battery.
  • the anolyte contains the plating additive described above, a sodium secondary battery according to an embodiment of the present invention having improved battery characteristics, cycle stability, and extended battery life by the plating additive is described in detail.
  • a sodium secondary battery according to an embodiment of the present invention may be a battery in which electrode deposition of metal occurs at the positive electrode during charging or discharging of the battery, and specifically, a battery in which electrodeposition of metal occurs at the positive electrode during discharge of the battery.
  • the electrodeposited metal may be a metal selected from at least one of a transition metal and a group 12 to 14 metals.
  • the electrochemical (charge and discharge) reaction of the battery is sodium; At least one metal selected from transition metals and Groups 12 to 14 metals (hereinafter, cathode active metals); And a halogen; and the anolyte is a solvent for dissolving sodium halides and anodic active metal halides together with the above-described plating additives, and an alkali metal, a transition metal, and a metal selected from the group consisting of at least one metal from Group 12-14. It may contain halides.
  • a sodium secondary battery comprises a negative electrode containing sodium;
  • a sodium ion conductive solid electrolyte separating the cathode and the anolyte.
  • the alkali metal includes lithium (Li), sodium (Na) and potassium (K)
  • the transition metal is titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe) , Cobalt (Co), nickel (Ni), and copper (Cu)
  • the metals of Groups 12 to 14 may include zinc (Zn), aluminum (Al), cadmium (Cd), and tin (Sn).
  • Sodium secondary battery according to an embodiment of the present invention is charged by the following reaction formula 1 and discharge is made by the following reaction formula 2, the sodium halide and the positive electrode active of the reaction formula 1 and reaction formula 2 during the charging and discharging of the battery
  • the metal halide may be in a liquid state in which the anolyte is dissolved.
  • M is a metal (anode active metal) selected from the group of transition metals and Group 12-14 metals
  • X is a halogen element
  • m is a natural number of 1 to 4.
  • m in Scheme 1 and Scheme 2 may be a natural number corresponding to the valence of the amount of the metal (M).
  • the positive electrode is one in the current collector itself or transition metal and group 12 to 14 metal group
  • the metal selected above may be a laminated or supported current collector. That is, based on the state of charge, the positive electrode may be made of only a current collector.
  • the positive electrode may be a current collector including a positive electrode active metal electrodeposited from the positive electrode solution.
  • the current collector including the positive electrode active metal is deposited or supported by a laminate of the positive electrode active metal, a film, a mesh or a porous film, and a laminate or a positive electrode active metal of the current collector. It may include a current collector.
  • the cathode active metal electrodeposited on the current collector is dissolved and dissolved in the anolyte solution as the cathode active metal ion. Ionization and reduction of the metal in which ions are electrodeposited again on the current collector (anode current collector) may be repeatedly performed.
  • reaction products or materials sodium halides, cathode active metal halides, etc.
  • the positive electrode and the charge and discharge reaction were described in detail.
  • the positive electrode active metal halide may be interpreted as ions and halogen ions of a metal (anode active metal) selected from one or more of the transition metal and the Group 12 to 14 metal group.
  • the uniformity, flatness, and resistivity of the positive electrode active metal electrodeposited on the positive electrode current collector can be improved.
  • the positive electrode active metal may be electrodeposited uniformly and homogeneously on a large current collector, and the electrodeposition speed may be improved, and the positive electrode active metal of non-uniform size may be prevented from being electrodeposited to the current collector without being uniform and dense.
  • electrodeposition of the non-uniform positive electrode active metal causes a non-uniform resistance for each region of the current collector, thereby deepening the partial electrodeposition of the positive electrode active metal.
  • a part of the electrodeposited positive electrode active metal is physically desorbed from the current collector.
  • the battery capacity can be permanently reduced.
  • the plating additive of the anolyte can prevent physical desorption of the electrodeposited cathode active metal to maintain stable charge / discharge cycle characteristics, and at the same time prevent a decrease in capacity with use time.
  • the anolyte may contain an inhibitor and an accelerator, and may further contain a planarizer.
  • an accelerator which promotes the reduction of metal ions and an inhibitor which adsorbs to the electrodeposition site for example, the surface of the current collector
  • the electrode active metal electrodeposited on the anode current collector Uniformity, flatness and specific resistance can be improved.
  • the positive electrode active metal may be electrodeposited to a uniform thickness in a large area.
  • the positive electrode solution may contain 1.5 ⁇ M to 150mM molar concentration, specifically 50 ⁇ M to 50mM molar concentration, more specifically 0.5mM to 30mM plating additives.
  • the content of the plating additive in the anolyte exceeds 150mM, there is a risk that the conductivity of sodium ions in the anolyte by the plating additive is reduced, and thus there is a risk that the efficiency of the battery is lowered.
  • the content of the plating additive in the anolyte is less than 1.5 ⁇ M, there is a risk that the charging and discharging reaction of the battery may have a uniform and flatness due to the above-described plating additive, and the effect of preventing a decrease in specific resistance is minimal.
  • the anolyte may contain an accelerator.
  • the molarity of the accelerator may improve the electrodeposition rate of the metal, but may be a concentration that can prevent the electrodeposition of the metal physically unstable to the positive electrode current collector by excessively increasing the speed.
  • the anolyte may contain 50 ⁇ M to 50 mM, more preferably 0.5 mM to 30 mM, and even more preferably 1 mM to 10 mM.
  • the anolyte contains an inhibitor and an accelerator
  • the molar ratio of the accelerator to the inhibitor may be 1: 0.01 to 2.
  • the molar ratio of the accelerator to the inhibitor affects the electrodeposition rate of the positive electrode active metal and the uniformity and compactness of the electrodeposition.
  • the molar ratio of the inhibitor to the accelerator is less than 0.01, excessively active in the current collector region where the adsorption of the inhibitor is insufficient.
  • the molar ratio of the inhibitor to the accelerator exceeds 2, there is a risk that the electrodeposition rate of the positive electrode active metal is too slowed by the inhibitor, so that the charge / discharge reaction of the battery may not be performed smoothly.
  • the molar ratio of accelerator to inhibitor may be from 1: 0.05 to 1.
  • the anolyte may further contain a flattening agent together with an inhibitor and an accelerator, and the molar ratio of the accelerator to the flattening agent may be 1: 0.01-2.
  • the leveling agent plays a similar role to the inhibitor, but it is mainly adsorbed at the edge of the pore inlet to prevent the inlet blockage so that the metal can be continuously deposited in the internal space.
  • the anode active metal is preferentially electrodeposited at the entrance (surface opening), so that the entrance is blocked first, so that it is difficult to enjoy the continuous metal electrodeposition effect inside, and the molar ratio of the planarizer to the accelerator exceeds two.
  • the electrodeposition rate of the positive electrode active metal may be too slow due to the planarizing agent, so that the charge / discharge reaction of the battery may not occur smoothly.
  • the molar ratio of accelerator to planarizer may be from 1: 0.05 to 1.
  • the concentration of the active material including the cathode active metal halide and / or sodium halide dissolved in the solvent of the anolyte is determined by a material capable of participating in the electrochemical reaction of the battery. It is directly related to the amount and can affect the energy capacity per unit volume of the cell and the ionic (including sodium ions) conductivity in the anolyte.
  • the positive electrode solution is 0.1 to 10 molar concentration (M), substantially, 0.5 to 10 molar concentration (M), more substantially 1 to 6 molar concentration (M), Even more substantially, it may contain an active material of 2 to 5 molarity (M).
  • M molar concentration
  • the active material contained in the anode solution may vary depending on the charged or discharged state of the battery, of Scheme 1 Charge based on the active material to be contained in the anolyte may be a MX m, based on the scheme 2 discharged state
  • the active material contained in the anolyte may be NaX.
  • the anolyte may contain additional sodium halide or sodium salt other than sodium halide that participates in the charge / discharge process of the battery.
  • concentration of an active material is explained in full detail.
  • the anolyte is 0.1 to 10 molar concentration (M), substantially, 0.5 to 10 molar concentration (M), more substantially 1 to 6 molar concentration ( M), even more substantially 2 to 5 molar concentration (M) of the positive electrode active metal halide.
  • the positive electrode active metal may be present in the positive electrode solution in the ionic phase or may be electrodeposited on the positive electrode current collector, and thus the positive electrode active metal ion concentration of the positive electrode solution may vary.
  • the concentration of the cargo may be the concentration on a state of charge basis.
  • the concentration of the positive electrode active metal halide is less than 0.1 based on the state of charge, the conductivity of ions participating in the electrochemical reaction of the battery, such as sodium ions, may be reduced, thereby reducing the efficiency of the battery. It can be too low.
  • the concentration of the positive electrode active metal halide exceeds 10 mol, the conductivity of sodium ions may be reduced by the metal ions having the same kind of charge as the sodium ions.
  • it is possible to control the ion conductivity in the anolyte by adding an additive which can increase the conductivity of sodium ions without being involved in the net reaction of the battery, such as an excess of sodium halide, which will be described later.
  • the concentration of the positive electrode active metal halide can be adjusted according to the capacity.
  • the concentration of sodium halide can also be determined by the concentration of the positive electrode active metal halide in the anolyte, but the sodium ions in the anolyte
  • the cathode may further include sodium halides together with the cathode active metal halide.
  • an excess of sodium ions and halide ions may be contained in an amount greater than that defined by the discharge reaction according to Scheme 2.
  • the anolyte may include anodic active metal halides and sodium halides dissolved in a solvent.
  • the charged anolyte may contain the cathode active metal halide and sodium halide dissolved in a solvent, and thus the charged liquid anode may contain metal ions, sodium ions, and halogen ions. .
  • the positive electrode solution in the state of charge may further contain 0.1 to 3 moles of sodium halide based on 1 mole of the positive electrode active metal halide.
  • the conductivity of sodium ions in the anolyte may be improved, and the charge and discharge reactions of Schemes 1 and 2 may be effectively performed in a faster time.
  • the battery operating temperature is low temperature, it is possible to ensure the conductivity and reaction rate of sodium ions.
  • the anolyte when the anolyte contains 0.1 to 10 mole concentration (M) of the positive electrode active material halide, the anolyte may contain a plating additive having a molar concentration of 1.5 ⁇ M to 150 mM.
  • the molar ratio of the accelerator to the inhibitor may be 1: 0.01 to 2
  • the molar ratio of the accelerator to the leveler may be 1: 0.01 to 2.
  • the cathode active metal halide may be a halide defined by the following Chemical Formula 1.
  • M is one or more selected from nickel (Ni), iron (Fe), copper (Cu), zinc (Zn), cadmium (Cd), titanium (Ti), aluminum (Al) and tin (Sn),
  • X is at least one selected from iodine (I), bromine (Br), chlorine (Cl) and fluorine (F)
  • m is a natural number of 1 to 4. In this case, m may be a natural number corresponding to the valence of the metal.
  • the alkali metal halide may be sodium halide
  • the sodium halide may be a halide defined by Formula 2 below.
  • X is one or more selected from iodine (I), bromine (Br), chlorine (Cl) and fluorine (F).
  • the solvent of the positive electrode may be a solvent that dissolves a metal halide and at the same time dissolves a sodium halide, but improves and charges ion conductivity of potassium ions. Improved stability of discharge cycle characteristics and storage characteristics that can prevent self-discharge Aspects
  • the non-aqueous organic solvent may be at least one selected from alcohols, polyhydric alcohols, heterocyclic hydrocarbons, amides, esters, ethers, lactones, carbonates, phosphates, sulfones and sulfoxides.
  • the ionic liquids are imidazolium based ionic liquids, piperidinium based ionic liquids, pyridinium based ionic liquids, pyrrolidinium based, ionic liquids, ammonium based ionic liquids, phosphonium based ions
  • One or more may be selected from ionic liquids and sulfonium based ionic liquids.
  • the liquid phase is stably maintained at the operating temperature and pressure of the secondary battery, and diffusion of sodium ions introduced through the solid electrolyte is easy, and unwanted side reactions occur.
  • 1-butyl-3-methylpyridinium bromide (1-Butyl-3-methylpyridinium bromide), 1-butyl-4-methylpyridinium bromide (1-Butyl-4-methylpyridinium bromide), 1-butylpyridinium bromide (1-Butylpyridinium bromide), 1-butyl-2-methylpyridinium bromide (1-Butyl-2-methylpyridinium bromide), 1-hexylpyridinium bromide, 1-ethylpyridinium bromide, 1-propyl-2-methylpyridinium bromide (1-Propyl-2-methylpyridinium bromide), 1-propyl-3-methylpyridinium bromide (1-Propyl-3-methylpyridinium bromide), 1-propyl-4-methylpyridinium bromide (1-Propyl-4-methylpyridinium bromide), 1-propylpyridinium bromide,
  • the solvent of the anolyte may further include a heterogeneous solvent having miscibility with the above-described solvent, an example of such a hetero solvent, ethylene carbonate (ethylene carbonate), Propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate, dimethyl carbonate, diethyl carbonate, di (2, 2,2-trifluoroethyl) carbonate, dipropyl carbonate, dibutyl carbonate, ethylmethyl carbonate, 2,2,2-trifluoroethyl methyl carbonate, methylpropyl carbonate, ethylpropylcarbonate, 2,2,2- Trifluoroethyl propyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, dimethyl ether, diethyl ether, dipro Et
  • the current collector (anode current collector) is in contact with the active material involved in the charging and discharging of the battery collects the current and serves to provide a current and a path for moving the current, the anolyte It can serve to provide an electrodeposition site (electrode) from the positive electrode active metal ion from.
  • the positive electrode may be made of only a current collector
  • the discharge state reference positive electrode may include a current collector and a positive electrode active metal electrode electrodeposited on the current collector.
  • the meaning that the positive electrode is impregnated in the anolyte may mean that the positive electrode is in physical contact with the anolyte, and when the current collector is porous, it may mean a state in which the positive electrode solution fills the pores of the current collector.
  • the current collector may be a porous conductor, and more particularly, the current collector may be a foam, film, mesh, felt or perforated film of a conductive material.
  • the current collector may be a conductive material including graphite, graphene, titanium, copper, platinum, aluminum, nickel, silver, gold, or carbon nanotubes that have excellent conductivity and are chemically stable during charging and discharging of a battery. It may be a composite coated or laminated with a different conductive material from each other.
  • the positive electrode active metal of the positive electrode active metal halide dissolved in the solvent during the discharge reaction is electrodeposited, and the positive electrode active metal electrodeposited during the charge reaction is dissolved in the solvent again.
  • Such electrodeposition and dissolution are electron sources (source and / Or in the region in contact with the sink).
  • the current collector may be homogeneous with the positive electrode active metal of the positive electrode active metal halide in terms of providing a preferential electrodeposition site for electrodeposition of the metal (ie, minimizing the energy barrier during heterogenous nucleation), or
  • the surface layer may be in the form of a foam, film, mesh, felt or perforated foil of conductive material formed thereon.
  • the negative electrode may include a negative electrode active material containing sodium, and the negative electrode active material may include a sodium metal or a sodium alloy.
  • the sodium alloy may be sodium and cesium, sodium and rubidium or mixtures thereof.
  • the negative electrode active material may be a liquid phase including a solid phase or a molten phase at the operating temperature of the cell.
  • the negative electrode active material may be molten sodium (molten Na), the operating temperature of the battery is 98 °C to 200 °C, substantially 98 °C to 150 °C, more substantially 98 °C to 130 °C.
  • the sodium ion conductive solid electrolyte provided between the positive electrode and the negative electrode may be a material that physically separates the positive electrode and the negative electrode and has a selective conductivity with respect to sodium ions. Solid electrolytes commonly used in the battery field for the selective conduction of ions are sufficient.
  • the solid electrolyte may be a sodium super ionic conductor (NaSICON), ⁇ -alumina, or ⁇ ′′ -alumina.
  • the sodium superion conductor may be Na— Zr-Si-O composite oxide, Na-Zr-Si-PO composite oxide, Y-doped Na-Zr-Si-PO composite oxide, Fe doped Na-Zr-Si-PO composite Oxides or mixtures thereof, and in particular, Na 3 Zr 2 Si 2 PO 12 , Na 1 + x Si x Zr 2 P 3-x O 12 (real number 1.6 ⁇ x ⁇ 2.4), Y or Fe Can comprise doped Na 3 Zr 2 Si 2 PO 12 , Y or Fe doped Na 1 + x Si x Zr 2 P 3-x O 12 (real numbers 1.6 ⁇ x ⁇ 2.4) or mixtures thereof.
  • the sodium secondary battery is a flat plate comprising a solid electrolyte of the flat plate shape It may have a tubular battery structure or a tubular battery structure comprising a tubular solid electrolyte of one end sealed.
  • the structure of the sodium secondary battery according to an embodiment of the present invention will be described in more detail based on FIG. 1 and based on the case where the negative electrode active material is molten sodium, but the present invention is limited by the physical form of the battery.
  • the sodium secondary battery according to the present invention may have a structure of a conventional sodium-based battery, such as a flat plate type or a tube type described later.
  • FIG. 1 illustrates an example of a structure of a sodium secondary battery according to an embodiment of the present invention.
  • a sodium secondary battery according to an embodiment of the present invention is sealed at a lower end thereof and opened at an upper end thereof.
  • the tube-shaped sodium ion conductive solid electrolyte hereinafter referred to as a solid electrolyte tube, the bottom of which is sequentially located from the outer side to the inner side of the metal housing 100 300
  • a safety tube 410 Located in the cylindrical metal housing 100, the metal housing 100, the tube-shaped sodium ion conductive solid electrolyte (hereinafter referred to as a solid electrolyte tube, the bottom of which is sequentially located from the outer side to the inner side of the metal housing 100) 300), a safety tube 410, and a wicking tube 420.
  • the wicking tube 420 positioned at the innermost side, ie, the center of the metal housing 100 may have a tube shape having a through hole 1 formed at the bottom thereof, and the safety tube 410 is outside the wicking tube 420.
  • the wicking tube 420 Located at a predetermined distance and may have a structure surrounding the wicking tube (420).
  • the cathode 400 including molten sodium is provided inside the wicking tube 420, and an empty space between the wicking tube 420 and the safety tube 410 through a through hole 1 formed under the wicking tube 420. It can have a structure that fills.
  • the double structure of the wicking tube 420 and the safety tube 410 prevents a violent reaction between the anode material and the cathode material when the solid electrolyte tube 300 breaks, and maintains a constant level of molten sodium even during discharge due to capillary force. It is a sustainable structure.
  • the solid electrolyte tube 300 is positioned to surround the safety tube 410 outside the safety tube 410, and may be a tube-shaped solid electrolyte having selective permeability to sodium ions (Na + ).
  • a space between the solid electrolyte tube 300 surrounding the safety tube 410 and the metal housing 100 may be provided with an anolyte 220 containing a plating additive and a positive electrode (a reference state current collector) 210.
  • the sodium secondary battery according to an embodiment of the present invention has a concentric structure and the wicking tube 420, the safety tube 410, the solid electrolyte tube 300, and the metal housing 100 are sequentially positioned from the inside to the outside.
  • the anode 400 containing the molten sodium is supported in the wicking tube 420, the electrolyte solution containing a plating additive in the space between the solid electrolyte tube 300 and the metal housing 100 ) May be provided, and a cathode (charge state reference current collector) 210 may be provided to be impregnated in the anolyte solution 220.
  • the anode 210 may be provided between the solid electrolyte tube 300 and the metal housing 100 by rolling, but the present invention is not limited by the shape of the anode. to be.
  • the sodium battery according to an embodiment of the present invention is located on the metal housing 100, the cover 110 for sealing the inside of the metal housing, has a ring shape and is located above the metal housing 100, the metal housing 100 And an electrode insulator 120 electrically insulating the solid electrolyte tube 300 from each other, and an electrode terminal 130 positioned around an upper end of the metal housing 100.
  • the internal pressure of the battery sealed by the cover 110 may be 15 psi or more immediately after manufacture, and the positive electrode 210 may be electrically connected to the metal housing 100.
  • a general negative electrode current collector may be introduced through the through hole of the cover 110 to be impregnated in a predetermined area in the negative electrode active material including molten sodium supported in the wicking tube 420.
  • a sodium secondary battery having a structure similar to that of FIG. 1 was prepared. Molten sodium was used as the cathode, ethylene glycol dissolved in a plating additive and sodium iodide (NaI) was used as the anolyte solution, nickel foam was used as the anode, and graphite felt was used as the anode and cathode current collector. Used.
  • the prepared positive electrode and the positive electrode solution may be prepared by dissolving nickel halide directly in the positive electrode solution on the basis of the discharge state or the charged state.
  • MPSA (3-mercapto-1-propane sulfonic acid) was used as an accelerator in the plating additive, PEG (polyethylene glycol) having a weight average molecular weight of 3350 was used as an inhibitor, and JGB (Janus Green B) was used as a flattening agent. .
  • the same cell was prepared as a reference cell except that no plating additive was added.
  • the molar concentration of sodium iodide (NaI) in the anolyte solution was 2.94 M
  • the molar concentration of the accelerator was 6 mM
  • the molar concentration of the inhibitor was 1 mM
  • the molar concentration of the planarizer was 1 mM.
  • FIG. 2 is a reference cell (None in FIG. 2), an accelerator is added (MPSA in FIG. 2, MPSA also shown below), an accelerator and an inhibitor is added (MPSA + PEG in FIG. 2, below) Also shown as MPSA + PEG) and the charge of the cells (MPSA + PEG + JGB of FIG. 2, also shown as MPSA + PEG + JGB in FIG. 2) with all of the accelerator, inhibitor and flattener added (FIG. 2 (a)) ) And discharge (Fig. 2 (b)). Characterization of the battery was carried out at 120 °C, charging and discharging was carried out under the conditions of C / 10, SOC 100%.
  • Figure 2 (a) shows the charge voltage according to the number of charge and discharge
  • Figure 2 (b) shows the discharge voltage according to the number of charge and discharge.
  • FIG. 3 is a diagram illustrating a change in voltage over time (FIG. 3A) and a change in voltage over time (FIG. 3B) during the 15th charge / discharge cycle.
  • the overvoltage was reduced in both charge and discharge compared to the case of the battery with the plating additive is added compared to the reference battery without the plating additive.
  • a marked improvement in properties by the accelerator, a battery containing both an accelerator, an inhibitor and a flat agent is more preferable.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne une batterie secondaire au sodium qui comprend : une anode contenant du sodium ; une cathode imprégnée avec une solution de cathode comprenant un additif de revêtement qui est au moins l'un choisi parmi un suppresseur, un niveleur, et un accélérateur ; et un électrolyte solide conducteur des ions sodium séparant l'anode et la cathode.
PCT/KR2013/011568 2012-12-13 2013-12-13 Batterie secondaire au sodium WO2014092493A2 (fr)

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KR10-2012-0145192 2012-12-13
KR20120145192 2012-12-13
KR1020130153901A KR102143461B1 (ko) 2012-12-13 2013-12-11 소듐 이차전지
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110438537A (zh) * 2019-08-09 2019-11-12 常州大学 一种新型高通量换热管及其制备方法

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Publication number Priority date Publication date Assignee Title
JPH0613106A (ja) * 1992-03-23 1994-01-21 Ngk Insulators Ltd ナトリウム−硫黄電池
JPH06342672A (ja) * 1992-11-18 1994-12-13 Ngk Insulators Ltd ナトリウム−硫黄電池及びその製造方法
KR20060000822A (ko) * 2004-06-29 2006-01-06 경상대학교산학협력단 상온형 나트륨 황화철 2차 전지
KR20110075094A (ko) * 2009-12-28 2011-07-06 한밭대학교 산학협력단 이중 전기도금법을 이용한 전기도금법 및 이로부터 형성되는 금속 박막
KR20120095949A (ko) * 2009-11-05 2012-08-29 세라마테크, 인코오포레이티드 나트륨 이온 전도성 세라믹 분리판을 갖는 고체-상태 나트륨계 2차 전지

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Publication number Priority date Publication date Assignee Title
JPH0613106A (ja) * 1992-03-23 1994-01-21 Ngk Insulators Ltd ナトリウム−硫黄電池
JPH06342672A (ja) * 1992-11-18 1994-12-13 Ngk Insulators Ltd ナトリウム−硫黄電池及びその製造方法
KR20060000822A (ko) * 2004-06-29 2006-01-06 경상대학교산학협력단 상온형 나트륨 황화철 2차 전지
KR20120095949A (ko) * 2009-11-05 2012-08-29 세라마테크, 인코오포레이티드 나트륨 이온 전도성 세라믹 분리판을 갖는 고체-상태 나트륨계 2차 전지
KR20110075094A (ko) * 2009-12-28 2011-07-06 한밭대학교 산학협력단 이중 전기도금법을 이용한 전기도금법 및 이로부터 형성되는 금속 박막

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110438537A (zh) * 2019-08-09 2019-11-12 常州大学 一种新型高通量换热管及其制备方法

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