WO2013154349A1 - Sodium secondary battery - Google Patents

Sodium secondary battery Download PDF

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Publication number
WO2013154349A1
WO2013154349A1 PCT/KR2013/003003 KR2013003003W WO2013154349A1 WO 2013154349 A1 WO2013154349 A1 WO 2013154349A1 KR 2013003003 W KR2013003003 W KR 2013003003W WO 2013154349 A1 WO2013154349 A1 WO 2013154349A1
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WO
WIPO (PCT)
Prior art keywords
acid
phenol
sodium
bis
group
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PCT/KR2013/003003
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French (fr)
Inventor
Jeong Soo Kim
Young Shol Kim
Je Hyun Chae
Won Sang KOH
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Sk Innovation Co.,Ltd.
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Priority claimed from KR1020130039159A external-priority patent/KR102061731B1/en
Publication of WO2013154349A1 publication Critical patent/WO2013154349A1/en

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
    • 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
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • 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 following disclosure relates to a sodium based secondary battery, and more particularly, to a sodium based secondary battery having significantly stable charging and discharging cycle characteristics.
  • a lead acid battery, a nickel hydrogen battery, a vanadium redox flow battery, and a lithium battery may be used.
  • the lead acid battery and the nickel hydrogen battery have significantly low energy density, they require a large space in order to store the same capacitance of energy therein.
  • vanadium redox flow battery a phenomenon that vanadium ions penetrate through an ion-exchange membrane is generated, such that energy efficiency and electrochemical stability are reduced.
  • the lithium battery having significantly excellent energy density and output characteristics is significantly advantageous in view of a technology.
  • the lithium battery is disadvantageous in view of economic efficiency in being used as a secondary battery for large scale power storage due to scarcity of a lithium material.
  • the sodium-nickel chloride battery should be operated at a temperature of at least 250°C or more, and the sodium-sulfur battery should be operated at a high temperature of at least 300°C or more. Therefore, the sodium based battery according to the related art is disadvantageous in view of temperature maintenance, sealability maintenance, safety, and economic efficiency in manufacturing or operating thereof and is continuously used to be repeatedly charged and discharged, such that it is rapidly deteriorated.
  • An object of the present invention is to provide a sodium based secondary battery having significantly improved charging and discharging characteristics, particularly, a sodium based secondary battery capable of preventing deterioration of battery characteristics even in the case of being repeatedly charged and discharged at an operation temperature of 100 to 200°C.
  • a sodium based secondary battery includes: an anode containing sodium; a catholyte solution containing a sodium salt and a medium defined by the following Chemical Formula 1; a cathode contacting the catholyte solution; and a solid electrolyte provided between the anode and catholyte solution and having sodium ion conductivity.
  • Each Y in Chemical Formula 1 may be independently selected from a group consisting of -OH and -C(O)OH.
  • -A- in Chemical Formula 1 may be a substituted or unsubstituted radical selected from a group consisting of C2-30 aliphatic, C2-30 hetero aliphatic, 6- to 12-membered aryl, 3- to 12-membered heterocyclic, 5-12-membered heteroaryl, polyolefin, polyester, polyether, polycarbonate, polyoxymethylene, and a mixture of at least two thereof.
  • n in Chemical Formula 1 may be 1 to 4.
  • the medium may include polyhydric alcohol or hydroxy acid.
  • the medium may include one or at least two of the materials selected from a group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-propane-1 ,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexaned
  • the medium may include one or at least two of the materials selected from a group consisting of 4,4'-(1-methylethyliden)bis[cyclohexanol], 2,2'-methylenebis[phenol], 4,4'-methylenebis[phenol], 4,4'-(phenylmethylene)bis[phenol], 4,4'-(diphenylmethylene)bis[phenol], 4,4'-(1,2-ethanediyl)bis[phenol], 4,4'-(1,2-cyclohexanediyl)bis[phenol], 4,4'-(1,3- cyclohexanediyl)bis[phenol], 4,4'-(1,4- cyclohexanediyl)bis[phenol], 4,4'-ethyllidendbis[phenol], 4,4'-(1-phenylethylidene)bis[phenol], 4,4'-propylidenbis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'-(1-methyl
  • the medium may include one or at least two of the materials selected from a group consisting of glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid, mandelic acid, 3-hydroxypropionic acid, DL-3-hydroxybutyric acid, D-3-hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3-hydroxyvaleric acid, L-3-hydroxyvaleric acid, salicylic acid, salicylic acid derivatives, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.
  • the sodium salt may include a sodium salt defined by the following Chemical Formula 2.
  • R in Chemical Formula 2 may be hydrogen; or a straight or branched chain C1 to C7 alkyl group).
  • the anode may include metallic sodium, and the cathode may include nickel hydroxide.
  • the catholyte solution may include 5 to 70 weight % sodium salt.
  • An operation temperature of the sodium based secondary battery may be 100 to 200°C.
  • the sodium based secondary battery according to the exemplary embodiment of the present invention may have significantly excellent and stable charging and discharging cycle characteristics and prevent deterioration of battery characteristics due to repeatedly charging and discharging operations. Even in the case in which the battery is charged and discharged 500 times or more, the deterioration of the battery characteristics may be hardly generated.
  • Figure 1 is a cross-sectional view schematically showing a sodium based secondary battery according to an embodiment of the present invention.
  • Figure. 2 is charge and discharge characteristics of a sodium secondary battery according to an embodiment of the present invention.
  • the sodium based secondary battery according to the exemplary embodiment of the present invention includes an anode containing sodium; a catholyte solution containing sodium salts and medium defined by the following Chemical Formula 1; a cathode contacting the catholyte solution; and a solid electrolyte provided between the anode and the catholyte solution and having sodium ion conductivity.
  • -A- in the Chemical Formula 1 is a substituted or unsubstituted radical selected from a group consisting of C2-30 aliphatic, C2-30 hetero aliphatic, 6- to 12-membered aryl, 3- to 12-membered heterocyclic, 5-12-membered heteroaryl, polyolefin, polyester, polyether, polycarbonate, polyoxymethylene, and a mixture of at least two thereof.
  • substituted means that at least one hydrogen of a designated residue is replaced by an appropriated substituent.
  • a "substituted” group may have a substituent appropriate for each substitutable position of the group, and in the case in which at least one of position in an arbitrary predetermined structure may be substituted with at least one of the substituent selected from a specific group, the substituents may be the same as or different from each other at all positions.
  • Composition of the substituent may be stable or to form a compound capable of being chemically composed.
  • the appropriated monovalent substituent of R ⁇ may be independently halogen; -(CH 2 ) 0-2 R ⁇ -(haloR ⁇ ), -(CH 2 ) 0-2 OH, -(CH 2 ) 0-2 OR ⁇ , -(CH 2 ) 0-2 CH(O R ⁇ ) 2 ; -O(haloR ⁇ ), -CN, -N 3 , -(CH 2 ) 0-2 C(O)R ⁇ , -(CH 2 ) 0-2 C(O)OH, -(CH 2 ) 0-2 C(O)OR ⁇ , -(CH 2 ) 0-4 C(O)N(R ⁇ ) 2 ; -(CH 2 ) 0-2 SR ⁇ , -(CH 2 ) 0-2 SH, -(CH 2 ) 0-2 NH 2 ,
  • An appropriate divalent substituent bonded to substitutable carbon adjacent to the substituted group may include -O(CR * 2 ) 2-3 O-(here, R * each independently may be selected from a hydrogen, C1-6 aliphatic that may be substituted as defined, 5- to 6-membered saturated or partially unsaturated ring that is not substituted and independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring).
  • An appropriate substituent of the aliphatic group of R * may include halogen, -R ⁇ , -(halo R ⁇ ), -OH, -O R ⁇ , -O(haloR ⁇ ), -CN, -C(O)OH, -C(O)OR ⁇ , -NH 2 , -NHR ⁇ , -NR ⁇ 2 , or -NO 2 (here, each R ⁇ is not substituted or substituted only with at least one halogen in the case in which "halo" is added in front of the R ⁇ ,and independently is a C1-4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0-1 Ph, or 5- to 6-membered saturated or partially unsaturated ring that independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring).
  • An appropriate substituent of substitutable nitrogen of the substituted group may include -R + , -NR + 2 , -C(O)R + , -C(O)OR + , -C(O)C(O)R + , -C(O)CH 2 C(O)R + , -S(O) 2 R + , -S(O) 2 NR + 2 , -C(S)NR + 2 , -C(NH)NR + 2 , or -N(R + )S(O) 2 R + (here, R + each independently hydrogen, C1-6 aliphatic that may be substituted as defined, -OPh that is not substituted, or 5- to 6-membered saturated or partially unsaturated ring that is not substituted and independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring, or two R + may form each independently 3- to 12-membered saturated or partially unsaturated ring that is not substituted and independently has 0 to
  • An appropriate substituent of the aliphatic group of R + may include independently halogen, -R ⁇ , -(halo R ⁇ ), -OH, -OR ⁇ , -O(haloR ⁇ ), -CN, -C(O)OH, -C(O)OR ⁇ , -NH 2 , -NHR ⁇ , -NR ⁇ 2 , or -NO 2 (here, each R ⁇ is not substituted or substituted only with at least one halogen in the case in which "halo" is added in front of the R ⁇ ,and independently may be a C1-4 aliphatic, -CH 2 Ph, -O(CH 2 ) 0-1 Ph, or a 5- to 6-membered saturated or partially unsaturated ring that independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring).
  • Halo and halogen may indicate an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodo, -I).
  • the aliphatic or aliphatic group indicates a hydrocarbon residue that may be a straight (that is, non-branched) chain, a branched chain, or cyclic (fused, bridged, and spiro-fused polycyclic are included) and may be completely saturated or contain at least one unsaturated unit, but is not aromatic.
  • the aliphatic group may contain 1 to 30 carbon atoms. In a specific aspect, the aliphatic group may contain 1 to 12 carbon atoms. In a specific aspect, the aliphatic group may contain 1 to 8 carbon atoms. In a specific aspect, the aliphatic group may contain 1 to 6 carbon atoms.
  • the aliphatic group may contain 1 to 5 carbon atoms, in another specific aspect, the aliphatic group may contain 1 to 4 carbon atoms, in still another specific aspect, the aliphatic group may contain 1 to 3 carbon atoms, and in still another specific aspect, the aliphatic group may contain 1 and 2 carbon atoms.
  • the aliphatic group may include straight chain or branched chain alkyl, alkenyl, and alkynyl groups, and mixtures thereof (for example, (cycloalkyl)alkyl, (cycloalkenyl)akyl, or (cycloalkyl)alkenyl), but is not limited thereto.
  • the aliphatic group may be C1-C20 alkanediol, C2-C20 alkantriol, substituted C2-C20 alkanediol, or substituted C2-C20 alkantriol.
  • Unsaturation may mean that the residue has at least one double bond or tripled bond.
  • Aryl may indicate a monocyclic or polycyclic ring system having a total of 5 to 20 ring circles, wherein in this system, at least one ring is aromatic, and each ring may contain 3 to 12 ring circles.
  • the Term "aryl” may be used mixed with the term "aryl ring".
  • aryl may include phenyl, biphenyl, naphthyl, anthraxyl, and the like, but is not limited thereto.
  • aryl may indicate an aromatic ring system capable of containing at least one substituent.
  • a group having an aromatic ring fused to at least one of the additional ring such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenanthridinyl, tetrahydronaphtyl, and the like, may be included in a range of aryl.
  • 6- to 10-membered aryl and C6-10 aryl may indicate phenyl or 8- to 10-membered polycyclic aryl ring.
  • 6- to 12-membered aryl may indicate phenyl or 8- to 12-membered polycyclic aryl ring.
  • C6-14 aryl may indicate phenyl or 8- to 14-membered polycyclic aryl ring.
  • Heteroaryl and heteroar- may indicate a group having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms, 6, 10, or 14 ⁇ electrons shared in a cyclic arrangement, and 1 to 5 hetero atoms except for a carbon atom.
  • the hetero atom may indicate nitrogen, oxygen, or sulfur and include nitrogen or sulfur in an arbitrarily oxidized form and basic nitrogen in an arbitrarily quaternized form.
  • Heteroaryl group may include thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl, phtheridinyl, but is not limited thereto.
  • Heteroaryl and heteroar- may indicate a group in which hetero aromatic ring is fused to at least one aryl, cycloaliphatic, or heterocyclyl ring, and a radical or a bonding point is positioned on hetero aromatic ring.
  • a nonrestrictive example may include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazine-3(4H)-on.
  • Heteroaryl group may be a monocyclic or bicyclic. Heteroaryl may be used mixed with the term “heteroaryl ring”, “heteroaryl group” or “heteroaromatic”, and all of these terms may include an arbitrarily substituted ring.
  • Heterocycle, heterocyclyl, heterocylic radica, and heterocyclic ring may be used mixed with each other and be a stable 5- to 7-membered monocyclic or 7- to 14-membered polycyclic heterocyclic residue that is saturated or partially unsaturated and has at least one, preferably 1 to 4 hetero atoms as defined above except for a carbon atom.
  • nitrogen may include substituted nitrogen.
  • nitrogen may be N (for example, such as 3,4-dihydro-2H-pyrolyl), NH (for example, such as pyrolidinyl), or +NR (for example, such as N-substituted pyrolidinyl).
  • N for example, such as 3,4-dihydro-2H-pyrolyl
  • NH for example, such as pyrolidinyl
  • +NR for example, such as N-substituted pyrolidinyl
  • 3- to 7-membered heterocyclic may indicate 3- to 7-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 hetero atoms independently selected from nitrogen, oxygen, or sulfur.
  • 3- to 8-membered heterocyclic may indicate 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 hetero atoms independently selected from nitrogen, oxygen, or sulfur.
  • the term 3- to 12-membered heterocyclic may indicate 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 hetero atoms independently selected from nitrogen, oxygen, or sulfur or 7- to 12-membered saturated or partially unsaturated polycyclic heterocyclic ring having 1 to 3 hetero atoms independently selected from nitrogen, oxygen, or sulfur.
  • 3- to 14-membered heterocyclic may indicate 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 hetero atoms independently selected from nitrogen, oxygen, or sulfur or 7- to 14-membered saturated or partially unsaturated polycyclic heterocyclic ring having 1 to 3 hetero atoms independently selected from nitrogen, oxygen, or sulfur.
  • an arbitrary hetero atom or a carbon atom may be bonded to a pendant group thereof to form a stable structure, and some of the ring atoms may be arbitrarily substituted.
  • An example of this saturated or partially unsaturated heterocyclic radical may include tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpolinyl, and quinuclidinyl, but is not limited thereto.
  • heterocycle, heterocyclyl, hetercyclyl ring, heterocyclic group, heterocyclic residue, and heterocyclic radical may be used mixed with each other and indicate a group in which the heterocyclic ring is fused to at least one aryl, heteroaryl, or cycloaliphatic ring (for example, indolyl, 3H-indolyl, chromanyl, phenantridinyl, or tetrahydroquinolinyl) and a radical or a bonding point is positioned on hetero cyclic ring.
  • Heterocyclyl group may be a monocyclic or bicyclic.
  • heterocyclylalkyl may indicate an alkyl group that is substituted by heterocyclyl, and alkyl and heterocyclyl portions may be independently arbitrarily substituted.
  • Partial unsaturation may indicate a ring residue including at least one double bond or triple bond.
  • an acidic hydrogen atom bonded to anyone of a functional group Y may be substituted with a metal atom or an organic positive ion.
  • -C(O)OH may be substituted with -C(O)O - Na + , -C(O)O - N + (R) 4 , -C(O)O - (Ca 2 + ) 0.5 , -C(O)O - PPN + , -SH, -S - Na + , or the like.
  • -OH may be substituted with -O - Na + , or the like.
  • the functional group Y may be hydroxyl or hydroxyl salt.
  • each of the hydroxyl groups may be primary alcohol or secondary alcohol, and the hydroxyl group may be bonded to an aromatic or hetero aromatic ring.
  • the hydroxyl group may be phenol, or may be benzylic, allylic, or propargylic.
  • the hydroxyl group may be a portion of carbohydrate, polyether, polyester, polyvinyl alcohol, a polymer such as hydroxyl-functionalized polyolefin, hydroxyl-terminated polyolefin, or oligomer.
  • the medium may be polyhydric alcohol.
  • the polyhydric alcohol may be diol, dihydric alcohol, trihydric alcohol, or higher polyol.
  • n may be 1, and both of the Y groups may be the hydroxyl group (that is, the medium is diol).
  • two hydroxyl groups may be on adjacent carbons (that is, medium is glycol).
  • two hydroxyl groups may be on non-adjacent carbons.
  • two hydroxyl groups may be on opposite distal ends of a chain (that is, medium is ⁇ - ⁇ diol). This ⁇ - ⁇ diol may include C3 to C20 aliphatic chain.
  • this ⁇ - ⁇ diol may include polyether, (that is, -A- is a polyether chain), be hydroxyl-terminated polyolefin (that is, -A- is a polyolefin chain), and include paraformaldehyde (that is, -A- is polyoxymethylene).
  • n is 1, and one Y group may be -OH, the other Y group may be selected from a group consisting of -SH, -C(O)OH, -NHR 1 , and -C(O)NHR 1 .
  • n is 1, one Y group may be -OH, and the other Y group may be -C(O)OH.
  • n is 1, one Y group may be -OH, and the other Y group may be -SH.
  • n is 1, one Y group may be -OH, and the other Y group may be -NHR 1 .
  • n is 2, and each Y group may be -OH.
  • n is 2, and a third Y group may be selected from a group consisting of -SH, -C(O)OH, -NHR 1 , and -C(O)NHR 1 .
  • n is 2, and one Y group may be -OH, other two Y groups may be independently selected from a group consisting of -SH, -C(O)OH, -NHR 1 , and -C(O)NHR 1 .
  • the medium in the case in which the medium is polyhydric alcohol, the medium may include a natural substance such as sugar alcohol, carbohydrate, sugars, polysaccharides, starch, starch derivatives, lignin, lignan, partially hydrolyzed triglyceride, or the like, and well known derivatives of anyone thereof.
  • a natural substance such as sugar alcohol, carbohydrate, sugars, polysaccharides, starch, starch derivatives, lignin, lignan, partially hydrolyzed triglyceride, or the like, and well known derivatives of anyone thereof.
  • the medium may contain diol, wherein diol may include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-propane-1 ,3-diol, 2-butyl-2 -ethyl-propane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexaned
  • the medium may contain alkoxide derived from a compound selected from a group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, higher poly(ethylene glycol), dipropylene glycol, tripropylene glycol, and higher poly (propylene glycol).
  • the higher poly(ethylene glycol) compound may have a number average molecular weight of 220 to 2000g/mol.
  • the higher poly(propylene glycol) compound may have a number average molecular weight of 234 to 2000g/mol.
  • the medium may contain diol, wherein diol may include 4,4'-(1-methylethyliden)bis[cyclohexanol], 2,2'-methylenebis[phenol], 4,4 '-methylenebis[phenol], 4,4'-(phenylmethylene)bis[phenol], 4,4'-(diphenylmethylene)bis[phenol], 4,4'-(1,2-ethanediyl)bis[phenol], 4,4'-(1,2-cyclohexanediyl)bis[phenol], 4,4'-(1,3- cyclohexanediyl)bis[phenol], 4,4'-(1,4- cyclohexanediyl)bis[phenol], 4,4'-ethyllidendbis[phenol], 4,4'-(1-phenylethylidene)bis[phenol], 4,4'-propylidenbis[phenol], 4,4'-cyclohexyliden
  • the medium may contain triol, wherein triol may include aliphatic triol having a molecular weight of 500 or less similar such as trimethylolethan, trimethylolpropane; glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; tris(2-hydroxyethyl)isocyanurate; hexadydro1,3,5-tris(hydroxyethyl)-s-triazine; 6-methylheptane-1,3,5-triol; polypropylene oxide triol; or polyester triol.
  • triol may include aliphatic triol having a molecular weight of 500 or less similar such as trimethylolethan, trimethylolpropane; glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; tris(2-hydroxyethyl)isocyanurate; hexadydro1,3,5-tris(hydroxyethyl)-s-triazin
  • the medium may contain tetraol, for example, erythritol, pentaerythritol, 2,2'-dihydroxymethyl-1,3-propandiol, or 2,2'-(oxydimethylene)bis-(2-ethyl-1,3-propandiol).
  • tetraol for example, erythritol, pentaerythritol, 2,2'-dihydroxymethyl-1,3-propandiol, or 2,2'-(oxydimethylene)bis-(2-ethyl-1,3-propandiol).
  • At least one of the Y group of the medium may be amine.
  • the Y group may be primary amine, secondary amine, aniline or aniline derivatives, or a N-H group which is a portion of heterocycle.
  • the medium may be polyamine and be diamine, triamine, tetramine, or higher amine oligomer.
  • At least one of the Y group may be amine, and at least one of the additional Y group may be independently selected from a group consisting of -OH, -SH, -C(O)OH, and -C(O)NHR 1 .
  • the medium may be amino alcohol, amino acid, amino thiol, or amino amide.
  • At least one of the Y group of the medium may be carboxylic acid or salts thereof.
  • all of Y group present in the medium may be carboxylic salts.
  • the medium may be biacid, triacid, or higher polyacid.
  • n may be 1, and both of Y groups may be carboxylic acid.
  • the medium may be biacid including phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or azelaic acid.
  • the medium may be triacid including citric acid, isocitric acid, cis- or trans-aconitic acid, propan-1,2,3-tricarboxylic acid, or trimesic acid.
  • At least one of the Y group may be carboxylic acid, and at least one of the additional Y group may be independently selected from a group consisting of -OH, -SH, NHR 1 , and -C(O)NHR 1 .
  • the solvent may be amino acid and include a natural amino acid.
  • the solvent may be a peptide, wherein peptide may contain 2 to 20 amino acid residues.
  • the medium may be thiolic acid or hydroxy acid.
  • the hydroxyl acid may be alpha-hydroxy acid.
  • the alpha-hydroxy acid may be selected from a group consisting of glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid and mandelic acid.
  • the hydroxyl acid may be beta-hydroxy acid.
  • the beta-hydroxy acid be selected from a group consisting of 3-hydroxypropionic acid, DL-3-hydroxybutyric acid, D-3-hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3-hydroxyvaleric acid, L-3-hydroxyvaleric acid, and salicylic acid and salicylic acid derivatives.
  • the hydroxy acid may be ⁇ - ⁇ hydroxyl acid.
  • the ⁇ - ⁇ hydroxyl acid may be selected from a group consisting of an unsubstituted or substituted C3-20 aliphatic ⁇ - ⁇ hydroxyl acids.
  • the ⁇ - ⁇ hydroxy acid may be polyester oligomer ester.
  • the medium may be a carboxylate salt.
  • the carboxylate salt may be a Group 1 metal salt or Group 2 metal salt.
  • At least one of the Y group of the medium may be thiol.
  • at least one of the Y group may be primary thiol, and at least one of the Y group may be secondary or tertiary thiol.
  • at least one of the Y group may be thiophenol or thiophenol derivatives.
  • the medium may be polythiol, that is, dithiol, trithiol, or, higher thiol oligomer.
  • At least one of the Y group may be thiol, and at least one of the additional Y group may be independently selected from a group consisting of -OH, -NHR 1 , -C(O)OH, and -C(O)NHR 1 .
  • the medium may be thio alcohol, amino thiol, thiol carboxylic acid.
  • At least one of the Y group may be an active NH-containing functional group.
  • a nitrogen atom of the active NH-containing functional group may be a nucleophile.
  • the active NH-containing functional group may be selected from a group consisting of C-bonded amide, N-bonded amide, O-bonded carbamate, N-bonded carbamate, urea, guanidine, amidine, hydrazone, and N- or C-bonded thioamide.
  • at least one of the Y group may be primary amide.
  • the catholyte solution may selectively include a material according to Chemical Formula 1 dissolved therein or further include a solvent miscibility with the material according to Chemical Formula 1.
  • the catholyte solution may further contain a material selected from a group consisting of ester, nitrile, ketone, aromatic hydrocarbon, ether, amine, and a mixture of at least two thereof.
  • an operation temperature of the sodium based secondary battery may be 200°C or less, substantially 100 to 200°C, and more substantially 100 to 150°C.
  • the sodium salt contained in the catholyte solution may include a sodium salt satisfying Chemical Formula 2.
  • R of Chemical Formula 2 is hydrogen; or a straight or branched chain C1 to C7 alkyl group.
  • the sodium salt contained in the catholyte solution may directly participate in charging and discharging reaction of the battery simultaneously with serving to smoothly moving sodium ions introduced through a solid electrolyte.
  • net reaction according to the following reaction formula 1 may be generated by the sodium salt.
  • the cathode containing nickel contacts the catholyte solution.
  • the catholyte solution contains the sodium salt of the reaction formula 1
  • nickel contained in the cathode may be changed into nickel compound as shown in the reaction formula 2
  • the nickel compound may be changed again into nickel metal as shown in the reaction formula 3.
  • the sodium salt contained in the catholyte solution may include a sodium salt according to Chemical Formula 2.
  • R of Chemical Formula 2 is hydrogen; or a straight or branched chain C1 to C7 alkyl group.
  • the sodium salt contained in the catholyte solution may be sodium acetate, sodium formate, or a mixture thereof.
  • a content of the sodium salt in the catholyte solution may be 5 to 70 weight %, preferably 10 to 70 weight %, and more preferably 20 to 63 weight %.
  • the catholyte solution may contain sodium acetate.
  • a content of the sodium acetate in the catholyte solution may be 5 to 70 weight %, preferably 10 to 70 weight %, and more preferably 20 to 63 weight %.
  • the catholyte solution may contain sodium formate.
  • a content of the sodium formate in the catholyte solution may be 5 to 70 weight %, preferably 10 to 70 weight %, and more preferably 20 to 63 weight %.
  • the amount of sodium salt capable of participating in the electrochemical reaction is insufficient, such that a charging and discharging speed may be reduced and an energy capacity per unit volume may be reduced in the entire battery, and ionic conductivity in the solution is low, such that a resistance value may be increased.
  • conductivity of the sodium ion may be reduced by a precipitate.
  • the cathode may include a foam, a film, a mesh, a felt, or a perforated film.
  • the cathode may include a nickel or nickel containing alloy foam, film, mesh, felt or perforated film.
  • the cathode (based on the discharging state) may be pure nickel; an alloy containing nickel; a laminate in which pure nickel or the nickel alloy and a conductive material are stacked; or a perforated conductor on which metal particles containing nickel are supported.
  • the alloy containing nickel in the case in which the cathode is the alloy containing nickel, the alloy containing nickel may be at least one of the alloy selected from nickel-copper alloy and nickel-iron alloy and substantially, be an alloy containing 0.01 to 99.9 weight% nickel.
  • pure nickel or the nickel alloy may contact a surface of a perforated conductor to thereby be stacked thereon in a foam, a film, a mesh, a felt, a perforated film, or a bar type or be inserted into the perforated conductor.
  • the cathode may be the perforated conductor having the nickel containing metal particles supported thereon or coated with the nickel containing metal particles.
  • the perforated conductor any material that has excellent conductivity and is chemically stable at the time of charging and discharging of the battery may be used.
  • the perforated conductor may be graphite, graphene, or conductive carbon including a carbon nanotube and have a foam, film, mesh, felt or perforated film type.
  • the cathode and the catholyte solution contact each other, which includes a shape in which the cathode including nickel is immerged in the catholyte solution.
  • the cathode may be in a rolled state.
  • the solid electrolyte having sodium ion conductivity may include a solid electrolyte generally used in the battery in order to selectively conduct the sodium ion, for example, a Na super ionic conductor (NASICON).
  • NASHCON Na super ionic conductor
  • the NASICON may include Na-Zr-Si-O based complex oxide, Na-Zr-Si-P-O based complex oxide, Y-doped Na-Zr-Si-P-O based complex oxide, Fe-doped Na-Zr-Si-P-O based complex oxide, or a mixture thereof.
  • a substantial example may include Y- or Fe-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 (1.6 ⁇ x ⁇ 2.4), or a mixture thereof.
  • the sodium based secondary battery according to the exemplary embodiment of the present invention may have a structure of a general sodium-sulfur battery having fused sodium as the anode or a structure of a sodium-nickel hydroxide battery.
  • FIG. 1 is a view showing a structure of a sodium based secondary battery according to an exemplary embodiment of the present invention.
  • the sodium based secondary battery according to the exemplary embodiment of the present invention may include a cylindrical metal housing 100 having a closed lower end and an opened upper end, a solid electrolyte (hereinafter solid electrolyte tube 300) sequentially positioned from an outer side of the metal housing 100 toward an inner side thereof in the metal housing 100 and having a closed lower end in a tube shape, a safety tube 410, and a wicking tube 420.
  • solid electrolyte tube 300 solid electrolyte tube 300
  • the wicking tube 420 positioned at an innermost portion may have the tube shape in which a through-hole 1 formed at a lower end thereof, and the safety tube 410 may be positioned at an outer side of the wicking tube 420 and have a structure in which the safety tube 410 encloses the wicking tube 420 while being spaced apart from the wicking tube 420 by a predetermined distance.
  • An anode 400 including fused sodium is provided in the wicking tube 420 and has a structure in which it fills an empty space between the wicking tube 420 and the safety tube 410 through the through-hole 1 formed at a lower portion of the wicking tube 420.
  • a dual structure of the wicking tube 420 and the safety tube 410 is a structure capable of preventing violent reaction between cathode materials and anode materials at the time of damage of the solid electrolyte tube 300 and constantly maintaining a level of the fused sodium due to the capillary force even at the time of discharging.
  • the solid electrolyte tube 300 is positioned at the outer side of the safety tube 410 so as to enclose the safety tube 410 and may be the tube shaped solid electrolyte having selective permeability to the sodium ion (Na + ).
  • a space between the solid electrolyte tube 300 enclosing the safety tube 410 and the metal housing 100 may be provided with a catholyte solution 220 containing medium according to Chemical Formula 1 and sodium salts according to Chemical Formula 2 and a cathode 210 including nickel.
  • the sodium based secondary battery according to the exemplary embodiment of the present invention may have a concentric structure in which the wicking tube 420, the safety tube 410, the solid electrolyte tube 300, and the metal housing 100 are sequentially positioned from the inner side toward the outer side.
  • the anode 400 containing the fused sodium may be supported on the inner portion of the wicking tube 420
  • the catholyte solution 220 containing the sodium salt according to Chemical Formula 2 may be provided in the space between the solid electrolyte tube 300 and the metal housing 100
  • the cathode 210 including nickel may be provided so as to be impregnated in the catholyte solution 220.
  • the cathode 210 including nickel may be rolled and provided between the solid electrolyte tube 300 and the metal housing 100, but the present invention is not limited to a shape of the cathode.
  • the sodium based secondary battery according to the exemplary embodiment of the present invention may further include a cover 110 positioned at an upper portion of the metal housing 100 to close an inner portion of the metal housing, insulator 120 having a ring shape and positioned at an upper side of the metal housing 100 to electrically insulate the metal housing 100 form the solid electrolyte tube 300, and an electrode terminal 130 positioned at a circumference of an upper end of the metal housing 100.
  • internal pressure of the battery closed by the cover 110 may be 15psi or more, and the anode including the nickel impregnated in the catholyte solution may be electrically connected to the metal housing 100.
  • an anode current collector may be input through a through-hole of the cover 110 so as to be impregnated by a predetermined area in the fused sodium anode supported on the inner portion of the wicking tube 420.
  • FIG. 2 is a view obtained by measuring charge and discharge characteristics of a sodium secondary battery manufactured using nickel as a cathode, metal sodium as an anode, and glycerol in which 20 weight% of sodium formate is dissolved as a catholyte solution.
  • nickel mesh was used as the cathode and connected to a platinum line used as a current collector.
  • 635mg of the solution (catholyte solution) in which 20 weight% of sodium formate is dissolved in glycerol was injected.
  • NaSICON having a thickness of 1mm and an area of 2cm 2 was used as a solid electrolyte, and 100mg of the sodium metal was injected into the anode in an opposite side of the NaSICON solid electrolyte, thereby configuring the battery.
  • the charge and discharge characteristics shown in FIG. 2 were results obtained by heating the secondary battery manufactured as described above to 110°C and then flowing 5mA of current to charge and discharge the secondary battery for 4 hours, respectively.

Abstract

Provided is a sodium based secondary battery including: an anode containing sodium; a catholyte solution containing a sodium salt and a medium defined by the following Chemical Formula 1 Y-A-(Y)n; a cathode contacting the catholyte solution; and a solid electrolyte provided between the anode and the catholyte solution and having a sodium ion conductivity.

Description

SODIUM SECONDARY BATTERY
The following disclosure relates to a sodium based secondary battery, and more particularly, to a sodium based secondary battery having significantly stable charging and discharging cycle characteristics.
In accordance with a rapid increase in the use of renewable energy, the necessity for an energy storage device using a battery has rapidly increased. Among these batteries, a lead acid battery, a nickel hydrogen battery, a vanadium redox flow battery, and a lithium battery may be used. However, since the lead acid battery and the nickel hydrogen battery have significantly low energy density, they require a large space in order to store the same capacitance of energy therein.
Further, in the vanadium redox flow battery, a phenomenon that vanadium ions penetrate through an ion-exchange membrane is generated, such that energy efficiency and electrochemical stability are reduced.
The lithium battery having significantly excellent energy density and output characteristics is significantly advantageous in view of a technology. However, the lithium battery is disadvantageous in view of economic efficiency in being used as a secondary battery for large scale power storage due to scarcity of a lithium material.
In order to solve this problem, many attempts to use a sodium resource sufficiently present on Earth as a material of the secondary battery, have been conducted. As disclosed in Korean Patent Laid-open Publication No. 1996-0002926, a sodium-sulfur battery having a form in which a beta alumina having selective conductivity for a sodium ion is used, an anode contains sodium, and a cathode contains sulfur has been currently used as the large capacitor power storage device.
However, in an existing sodium based secondary battery such as the sodium-sulfur battery or sodium-nickel chloride battery, conductivity thereof and melting point of battery compositions should be considered. For example, the sodium-nickel chloride battery should be operated at a temperature of at least 250℃ or more, and the sodium-sulfur battery should be operated at a high temperature of at least 300℃ or more. Therefore, the sodium based battery according to the related art is disadvantageous in view of temperature maintenance, sealability maintenance, safety, and economic efficiency in manufacturing or operating thereof and is continuously used to be repeatedly charged and discharged, such that it is rapidly deteriorated.
An object of the present invention is to provide a sodium based secondary battery having significantly improved charging and discharging characteristics, particularly, a sodium based secondary battery capable of preventing deterioration of battery characteristics even in the case of being repeatedly charged and discharged at an operation temperature of 100 to 200℃.
In one general aspect, a sodium based secondary battery includes: an anode containing sodium; a catholyte solution containing a sodium salt and a medium defined by the following Chemical Formula 1; a cathode contacting the catholyte solution; and a solid electrolyte provided between the anode and catholyte solution and having sodium ion conductivity.
(Chemical Formula 1)
Y-A-(Y)n
(In Chemical Formula 1, the respective Ys may be the same as or different from each other and be independently selected from a group consisting of -OH, -C(O)OH, -C(OR1)OH, -OC(R1)OH, -NHR1, -NHC(O)R1, -NHC=NR1, -NR1C=NH, -NR1C(NR1 2)=NH, -NHC(NR1 2)=NR1, -NHC(O)OR1, -NHC(O)NR1 2, -C(O)NHR1, -C(S)NHR1, -OC(O)NHR1, -OC(S)NHR1, -SH, -C(O)SH, -B(OR1)OH, -P(O)a(R1)b(OR1)c(O)dH, -OP(O)a(R1)b(OR1)c(O)dH, -N(R1)OH, -ON(R1)H, =NOH, and =NN(R1)H, wherein R1 each independently may be -H or a substituted or unsubstituted radical selected from a group consisting of C1-20 aliphatic, C1-20 hetero aliphatic, 3- to 12-membered heterocyclic and 6- to 12-membered aryl, a and b may be each independently 0 or 1, c may be 0, 1, or 2, d may be 0 or 1, the sum of a, b, and c may be 1 or 2, an acidic hydrogen atom bonded to one of the Y may be substituted by a metal atom or organic positive ion, -A- may be covalent bonding or a multivalent residue, and n may be an integer of 1 to 10).
Each Y in Chemical Formula 1 may be independently selected from a group consisting of -OH and -C(O)OH.
-A- in Chemical Formula 1 may be a substituted or unsubstituted radical selected from a group consisting of C2-30 aliphatic, C2-30 hetero aliphatic, 6- to 12-membered aryl, 3- to 12-membered heterocyclic, 5-12-membered heteroaryl, polyolefin, polyester, polyether, polycarbonate, polyoxymethylene, and a mixture of at least two thereof.
n in Chemical Formula 1 may be 1 to 4.
The medium may include polyhydric alcohol or hydroxy acid.
The medium may include one or at least two of the materials selected from a group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-propane-1 ,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and poly propylene glycol.
The medium may include one or at least two of the materials selected from a group consisting of 4,4'-(1-methylethyliden)bis[cyclohexanol], 2,2'-methylenebis[phenol], 4,4'-methylenebis[phenol], 4,4'-(phenylmethylene)bis[phenol], 4,4'-(diphenylmethylene)bis[phenol], 4,4'-(1,2-ethanediyl)bis[phenol], 4,4'-(1,2-cyclohexanediyl)bis[phenol], 4,4'-(1,3- cyclohexanediyl)bis[phenol], 4,4'-(1,4- cyclohexanediyl)bis[phenol], 4,4'-ethyllidendbis[phenol], 4,4'-(1-phenylethylidene)bis[phenol], 4,4'-propylidenbis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'-(1-methylethylidene)bis[phenol], 4,4'-(1-methylpropylidend)bis[phenol], 4,4'-(1-ethylpropylidene)bis[phenol], 4,4'-cyclohexylidendbis[phenol], 4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9,diyldi-2,1-ethandiyl)bis[phenol], 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[phenol], 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis[phenol], phenolphthalein, 4,4'-(1-methylidend)bis[2-methylphenol], 4,4'-(1-methylethylidene)bis[2-(1-methylethyl)phenol], and 2,2'-methylenebis[4-methyl-6-(1-methylethyl) phenol].
The medium may include one or at least two of the materials selected from a group consisting of glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid, mandelic acid, 3-hydroxypropionic acid, DL-3-hydroxybutyric acid, D-3-hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3-hydroxyvaleric acid, L-3-hydroxyvaleric acid, salicylic acid, salicylic acid derivatives, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.
The sodium salt may include a sodium salt defined by the following Chemical Formula 2.
(Chemical Formula 2)
Figure PCTKR2013003003-appb-I000001
(R in Chemical Formula 2 may be hydrogen; or a straight or branched chain C1 to C7 alkyl group).
The anode may include metallic sodium, and the cathode may include nickel hydroxide.
The catholyte solution may include 5 to 70 weight % sodium salt.
An operation temperature of the sodium based secondary battery may be 100 to 200℃.
The sodium based secondary battery according to the exemplary embodiment of the present invention may have significantly excellent and stable charging and discharging cycle characteristics and prevent deterioration of battery characteristics due to repeatedly charging and discharging operations. Even in the case in which the battery is charged and discharged 500 times or more, the deterioration of the battery characteristics may be hardly generated.
Figure 1 is a cross-sectional view schematically showing a sodium based secondary battery according to an embodiment of the present invention.
Figure. 2 is charge and discharge characteristics of a sodium secondary battery according to an embodiment of the present invention.
Hereinafter, a sodium based secondary battery according to an exemplary embodiment of the present invention will be described in detail. Technical terms and scientific terms used in the present specification have the general meaning understood by those skilled in the art to which the present invention pertains unless otherwise defined, and a description for the known function and configuration obscuring the present invention will be omitted in the following description and the accompanying drawings.
The sodium based secondary battery according to the exemplary embodiment of the present invention includes an anode containing sodium; a catholyte solution containing sodium salts and medium defined by the following Chemical Formula 1; a cathode contacting the catholyte solution; and a solid electrolyte provided between the anode and the catholyte solution and having sodium ion conductivity.
[Chemical Formula 1]
Y-A-(Y)n
In Chemical Formula 1, the respective Ys may be the same as or different from each other and be independently selected from a group consisting of -OH, -C(O)OH, -C(OR1)OH, -OC(R1)OH, -NHR1, -NHC(O)R1, -NHC=NR1, -NR1C=NH, -NR1C(NR1 2)=NH, -NHC(NR1 2)=NR1, -NHC(O)OR1, -NHC(O)NR1 2, -C(O)NHR1, -C(S)NHR1, -OC(O)NHR1, -OC(S)NHR1, -SH, -C(O)SH, -B(OR1)OH, -P(O)a(R1)b(OR1)c(O)dH, -OP(O)a(R1)b(OR1)c(O)dH, -N(R1)OH, -ON(R1)H, =NOH, and =NN(R1)H, wherein R1 each independently is -H or a substituted or unsubstituted radical selected from a group consisting of C1-20 aliphatic, C1-20 hetero aliphatic, 3- to 12-membered heterocyclic and 6- to 12-membered aryl, a and b are each independently 0 or 1, c is 0, 1, or 2, d is 0 or 1, the sum of a, b, and c is 1 or 2, an acidic hydrogen atom bonded to one of the Y may be substituted by a metal atom or organic positive ion, -A- is covalent bonding or a multivalent residue, and n is an integer of 1 to 10.
In Chemical Formula 1, -A- in the Chemical Formula 1 is a substituted or unsubstituted radical selected from a group consisting of C2-30 aliphatic, C2-30 hetero aliphatic, 6- to 12-membered aryl, 3- to 12-membered heterocyclic, 5-12-membered heteroaryl, polyolefin, polyester, polyether, polycarbonate, polyoxymethylene, and a mixture of at least two thereof.
In describing the present invention, the term "substituted" means that at least one hydrogen of a designated residue is replaced by an appropriated substituent. Unless noted otherwise, a "substituted" group may have a substituent appropriate for each substitutable position of the group, and in the case in which at least one of position in an arbitrary predetermined structure may be substituted with at least one of the substituent selected from a specific group, the substituents may be the same as or different from each other at all positions. Composition of the substituent may be stable or to form a compound capable of being chemically composed.
A monovalent substituent appropriate for a substitutable carbon atom of the substituted group may be each independently halogen; -(CH2)0-4R˚; -(CH2)0-4OR˚; -O-(CH2)0-4C(O)OR˚; -(CH2)0-4CH(OR˚)2; -(CH2)0-4SR˚; -(CH2)0-4Ph(Ph=phenyl) that may be substituted by R˚; -(CH2)0-4O(CH2)0-1Ph that may be substituted by R˚; -CH=CHPh that may be substituted by R˚; -NO2; -CN; -N3; -(CH2)0-4N(R˚)2; -(CH2)0-4N(R˚)C(O)R˚; -N(R˚)C(S)R˚; -(CH2)0-4N(R˚)C(O)NR˚2; -N(R˚)C(S)NR˚2; -(CH2)0-4N(R˚)C(O)OR˚; -N(R˚)N(R˚)C(O)R˚; -N(R˚)N(R˚)C(O)NR˚2; -N(R˚)N(R˚)C(O)OR˚; -(CH2)0-4C(O)R˚; -C(S)R˚; -(CH2)0-4C(O)OR˚; -(CH2)0-4C(O)N(R˚)2; -(CH2)0-4C(O)SR˚; -(CH2)0-4C(O)OSiR˚3; -(CH2)0-4OC(O)R˚; -OC(O)(CH2)0-4SR-; SC(S)SR˚; -(CH2)0-4SC(O)R˚; -(CH2)0-4C(O)NR˚2; -C(S)NR˚2; -C(S)SR˚; -C(S)SR˚, -(CH2)0-4OC(O)NR˚2; -C(O)N(OR˚)R˚; -C(O)C(O)R˚; -C(O)CH2C(O)R˚; -C(NOR˚)R˚; -(CH2)0-4SSR˚; -(CH2)0-4S(O)2R˚; -(CH2)0-4S(O)2OR˚; -(CH2)0-4OS(O)2R˚; -S(O)2NR˚; (CH2)0-4S(O)R˚; -N(R˚)S(O)2NR˚2; -N(R˚)S(O)2R˚; -N(OR˚)R˚; -C(NH)NR˚2; -P(O)2R˚; -P(O)R˚2; -OP(O)R˚2; -OP(O)(OR˚)2; SiR˚3 ; -(C1-4 straight chain or branched chain alkylene)O-N(R˚)2; or -(C1-4 straight chain or branched chain alkylene)C(O)O-N(R˚)2 wherein each R˚ may be substituted as defined and be independently hydrogen, C1-8 aliphatic, -CH2Ph, -O(CH2)0-1Ph, 5- and 6-membered saturated or partially unsaturated ring having 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring, and two R˚s independently, together with interposed atom(s) thereof, may form 3- to 12-membered saturated or partially unsaturated ring that independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur and may be substituted as defined, or aryl monocyclic or polycyclic ring.
The appropriated monovalent substituent of R˚ (or a ring formed by independently selecting two R˚s together with the interposed atoms) may be independently halogen; -(CH2)0-2R˙-(haloR˙), -(CH2)0-2OH, -(CH2)0-2OR˙, -(CH2)0-2CH(O R˙)2; -O(haloR˙), -CN, -N3, -(CH2)0-2C(O)R˙, -(CH2)0-2C(O)OH, -(CH2)0-2C(O)OR˙, -(CH2)0-4C(O)N(R˙)2; -(CH2)0-2SR˙, -(CH2)0-2SH, -(CH2)0-2NH2, -(CH2)0-2NHR˙, -(CH2)0-2NR˙ 2, -NO2, -SiR˙ 3, -OSiR˙ 3, -C(O)SR˙ or -(C1-4 straight chain or branched chain alkylene)C(O)ORR˙, wherein each RR˙ is not substituted or substituted only with at least one halogen in the case in which "halo" is added in front of the R˙, and may be independently selected from a C1-4 aliphatic, -CH2Ph, -O(CH2)0-1Ph, or 5- to 6-membered saturated or partially unsaturated ring that independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring. A divalent substituent appropriate for a saturated carbon atom of R˙ may be include =O and =S.
An appropriate divalent substituent of a saturated carbon atom of the substituted group may be =O, =S, =NNR* 2, =NNHC(O)R*, =NNHC(O)OR*, =NNHS(O)2R*, =NR*, =NOR*O(C(R* 2))2-3O-, or -S(C(R* 2))2-3S-, wherein R* each independently may be selected from a hydrogen, C1-6 aliphatic that may be substituted as defined, or 5- to 6-membered saturated or partially unsaturated ring that is not substituted and independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring.
An appropriate divalent substituent bonded to substitutable carbon adjacent to the substituted group may include -O(CR* 2)2-3O-(here, R* each independently may be selected from a hydrogen, C1-6 aliphatic that may be substituted as defined, 5- to 6-membered saturated or partially unsaturated ring that is not substituted and independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring).
An appropriate substituent of the aliphatic group of R* may include halogen, -R˙, -(halo R˙), -OH, -O R˙, -O(haloR˙), -CN, -C(O)OH, -C(O)OR˙, -NH2, -NHR˙, -NR˙ 2, or -NO2(here, each R˙ is not substituted or substituted only with at least one halogen in the case in which "halo" is added in front of the R˙ ,and independently is a C1-4 aliphatic, -CH2Ph, -O(CH2)0-1Ph, or 5- to 6-membered saturated or partially unsaturated ring that independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring).
An appropriate substituent of substitutable nitrogen of the substituted group may include -R＋, -NR＋ 2, -C(O)R＋, -C(O)OR＋, -C(O)C(O)R＋, -C(O)CH2C(O)R＋, -S(O)2R＋, -S(O)2NR＋ 2, -C(S)NR＋ 2, -C(NH)NR＋ 2, or -N(R＋)S(O)2R＋ (here, R＋ each independently hydrogen, C1-6 aliphatic that may be substituted as defined, -OPh that is not substituted, or 5- to 6-membered saturated or partially unsaturated ring that is not substituted and independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring, or two R＋ may form each independently 3- to 12-membered saturated or partially unsaturated ring that is not substituted and independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl monocyclic or bicyclic ring, together with the interposed atom(s) thereof ).
An appropriate substituent of the aliphatic group of R＋ may include independently halogen, -R·, -(halo R·), -OH, -OR·, -O(haloR·), -CN, -C(O)OH, -C(O)OR·, -NH2, -NHR·, -NR· 2, or -NO2 (here, each R· is not substituted or substituted only with at least one halogen in the case in which "halo" is added in front of the R· ,and independently may be a C1-4 aliphatic, -CH2Ph, -O(CH2)0-1Ph, or a 5- to 6-membered saturated or partially unsaturated ring that independently has 0 to 4 hetero atoms selected from nitrogen, oxygen, or sulfur, or aryl ring).
Halo and halogen may indicate an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodo, -I).
The aliphatic or aliphatic group indicates a hydrocarbon residue that may be a straight (that is, non-branched) chain, a branched chain, or cyclic (fused, bridged, and spiro-fused polycyclic are included) and may be completely saturated or contain at least one unsaturated unit, but is not aromatic. The aliphatic group may contain 1 to 30 carbon atoms. In a specific aspect, the aliphatic group may contain 1 to 12 carbon atoms. In a specific aspect, the aliphatic group may contain 1 to 8 carbon atoms. In a specific aspect, the aliphatic group may contain 1 to 6 carbon atoms. In a specific aspect, the aliphatic group may contain 1 to 5 carbon atoms, in another specific aspect, the aliphatic group may contain 1 to 4 carbon atoms, in still another specific aspect, the aliphatic group may contain 1 to 3 carbon atoms, and in still another specific aspect, the aliphatic group may contain 1 and 2 carbon atoms. For example, the aliphatic group may include straight chain or branched chain alkyl, alkenyl, and alkynyl groups, and mixtures thereof (for example, (cycloalkyl)alkyl, (cycloalkenyl)akyl, or (cycloalkyl)alkenyl), but is not limited thereto. For example, the aliphatic group may be C1-C20 alkanediol, C2-C20 alkantriol, substituted C2-C20 alkanediol, or substituted C2-C20 alkantriol.
"Unsaturation" may mean that the residue has at least one double bond or tripled bond.
Aryl may indicate a monocyclic or polycyclic ring system having a total of 5 to 20 ring circles, wherein in this system, at least one ring is aromatic, and each ring may contain 3 to 12 ring circles. The Term "aryl" may be used mixed with the term "aryl ring". In a specific aspect of the present invention, aryl may include phenyl, biphenyl, naphthyl, anthraxyl, and the like, but is not limited thereto. For example, aryl may indicate an aromatic ring system capable of containing at least one substituent. A group having an aromatic ring fused to at least one of the additional ring such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenanthridinyl, tetrahydronaphtyl, and the like, may be included in a range of aryl. In a specific aspect, 6- to 10-membered aryl and C6-10 aryl may indicate phenyl or 8- to 10-membered polycyclic aryl ring. In a specific aspect, 6- to 12-membered aryl may indicate phenyl or 8- to 12-membered polycyclic aryl ring. In a specific aspect, C6-14 aryl may indicate phenyl or 8- to 14-membered polycyclic aryl ring.
Heteroaryl and heteroar- may indicate a group having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms, 6, 10, or 14 π electrons shared in a cyclic arrangement, and 1 to 5 hetero atoms except for a carbon atom. The hetero atom may indicate nitrogen, oxygen, or sulfur and include nitrogen or sulfur in an arbitrarily oxidized form and basic nitrogen in an arbitrarily quaternized form. Heteroaryl group may include thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl, phtheridinyl, but is not limited thereto. Heteroaryl and heteroar- may indicate a group in which hetero aromatic ring is fused to at least one aryl, cycloaliphatic, or heterocyclyl ring, and a radical or a bonding point is positioned on hetero aromatic ring. A nonrestrictive example may include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzothiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazine-3(4H)-on.
Heteroaryl group may be a monocyclic or bicyclic. Heteroaryl may be used mixed with the term "heteroaryl ring", "heteroaryl group" or "heteroaromatic", and all of these terms may include an arbitrarily substituted ring.
Heterocycle, heterocyclyl, heterocylic radica, and heterocyclic ring may be used mixed with each other and be a stable 5- to 7-membered monocyclic or 7- to 14-membered polycyclic heterocyclic residue that is saturated or partially unsaturated and has at least one, preferably 1 to 4 hetero atoms as defined above except for a carbon atom. In the case in which a ring atom of heterocycle is referred, nitrogen may include substituted nitrogen. For example, in a saturated or partially unsaturated ring having 0 to 3 hetero atoms selected from oxygen, sulfur, or nitrogen, nitrogen may be N (for example, such as 3,4-dihydro-2H-pyrolyl), NH (for example, such as pyrolidinyl), or +NR (for example, such as N-substituted pyrolidinyl). In a specific aspect, 3- to 7-membered heterocyclic may indicate 3- to 7-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 hetero atoms independently selected from nitrogen, oxygen, or sulfur. In a specific aspect, 3- to 8-membered heterocyclic may indicate 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 hetero atoms independently selected from nitrogen, oxygen, or sulfur. In a specific aspect, the term 3- to 12-membered heterocyclic may indicate 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 hetero atoms independently selected from nitrogen, oxygen, or sulfur or 7- to 12-membered saturated or partially unsaturated polycyclic heterocyclic ring having 1 to 3 hetero atoms independently selected from nitrogen, oxygen, or sulfur. In a specific aspect, 3- to 14-membered heterocyclic may indicate 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 2 hetero atoms independently selected from nitrogen, oxygen, or sulfur or 7- to 14-membered saturated or partially unsaturated polycyclic heterocyclic ring having 1 to 3 hetero atoms independently selected from nitrogen, oxygen, or sulfur.
In the Heterocyclic ring, an arbitrary hetero atom or a carbon atom may be bonded to a pendant group thereof to form a stable structure, and some of the ring atoms may be arbitrarily substituted. An example of this saturated or partially unsaturated heterocyclic radical may include tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl, dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpolinyl, and quinuclidinyl, but is not limited thereto. The terms heterocycle, heterocyclyl, hetercyclyl ring, heterocyclic group, heterocyclic residue, and heterocyclic radical may be used mixed with each other and indicate a group in which the heterocyclic ring is fused to at least one aryl, heteroaryl, or cycloaliphatic ring (for example, indolyl, 3H-indolyl, chromanyl, phenantridinyl, or tetrahydroquinolinyl) and a radical or a bonding point is positioned on hetero cyclic ring. Heterocyclyl group may be a monocyclic or bicyclic. The term heterocyclylalkyl may indicate an alkyl group that is substituted by heterocyclyl, and alkyl and heterocyclyl portions may be independently arbitrarily substituted.
Partial unsaturation may indicate a ring residue including at least one double bond or triple bond.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, an acidic hydrogen atom bonded to anyone of a functional group Y may be substituted with a metal atom or an organic positive ion. For example, -C(O)OH may be substituted with -C(O)O-Na+, -C(O)O-N+(R)4, -C(O)O-(Ca2 +)0.5, -C(O)O-PPN+, -SH, -S-Na+, or the like. For example, -OH may be substituted with -O-Na+, or the like.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the functional group Y may be hydroxyl or hydroxyl salt.
For example, each of the hydroxyl groups may be primary alcohol or secondary alcohol, and the hydroxyl group may be bonded to an aromatic or hetero aromatic ring.
For example, the hydroxyl group may be phenol, or may be benzylic, allylic, or propargylic. For example, the hydroxyl group may be a portion of carbohydrate, polyether, polyester, polyvinyl alcohol, a polymer such as hydroxyl-functionalized polyolefin, hydroxyl-terminated polyolefin, or oligomer.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the medium may be polyhydric alcohol.
For example, the polyhydric alcohol may be diol, dihydric alcohol, trihydric alcohol, or higher polyol.
For example, n may be 1, and both of the Y groups may be the hydroxyl group (that is, the medium is diol). For example, two hydroxyl groups may be on adjacent carbons (that is, medium is glycol). For example, two hydroxyl groups may be on non-adjacent carbons. For example, two hydroxyl groups may be on opposite distal ends of a chain (that is, medium is α-ω diol). This α-ω diol may include C3 to C20 aliphatic chain. For example, this α-ω diol may include polyether, (that is, -A- is a polyether chain), be hydroxyl-terminated polyolefin (that is, -A- is a polyolefin chain), and include paraformaldehyde (that is, -A- is polyoxymethylene).
For example, n may be 1, one Y group may be -OH, and the other Y group may be selected from a group consisting of -C(O)OH, -C(OR1)OH, -OC(R1)OH, -NHR1, -NHC(O)R1, -NHC(O)OR1, -C(O)NHR1, -C(S)NHR1, -OC(O)NHR1, -OC(S)NHR1, -SH, -C(O)SH, -B(OR1)OH, -P(O)a(R1)b(OR1)cOH, -OP(O)a(R1)b(OR1)cOH, -N(R1)OH, -ON(R1)H, =NOH, and =NN(R1)H.
For example, n is 1, and one Y group may be -OH, the other Y group may be selected from a group consisting of -SH, -C(O)OH, -NHR1, and -C(O)NHR1. For example, n is 1, one Y group may be -OH, and the other Y group may be -C(O)OH. For example, n is 1, one Y group may be -OH, and the other Y group may be -SH. For example, n is 1, one Y group may be -OH, and the other Y group may be -NHR1.
For example, n is 2, and each Y group may be -OH. For example, n is 2, and a third Y group may be selected from a group consisting of -SH, -C(O)OH, -NHR1, and -C(O)NHR1. For example, n is 2, and one Y group may be -OH, other two Y groups may be independently selected from a group consisting of -SH, -C(O)OH, -NHR1, and -C(O)NHR1.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, in the case in which the medium is polyhydric alcohol, the medium may include a natural substance such as sugar alcohol, carbohydrate, sugars, polysaccharides, starch, starch derivatives, lignin, lignan, partially hydrolyzed triglyceride, or the like, and well known derivatives of anyone thereof.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the medium may contain diol, wherein diol may include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-propane-1 ,3-diol, 2-butyl-2 -ethyl-propane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and 1,4-cyclohexanediethanol.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the medium may contain alkoxide derived from a compound selected from a group consisting of ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, higher poly(ethylene glycol), dipropylene glycol, tripropylene glycol, and higher poly (propylene glycol). The higher poly(ethylene glycol) compound may have a number average molecular weight of 220 to 2000g/mol. The higher poly(propylene glycol) compound may have a number average molecular weight of 234 to 2000g/mol.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the medium may contain diol, wherein diol may include 4,4'-(1-methylethyliden)bis[cyclohexanol], 2,2'-methylenebis[phenol], 4,4 '-methylenebis[phenol], 4,4'-(phenylmethylene)bis[phenol], 4,4'-(diphenylmethylene)bis[phenol], 4,4'-(1,2-ethanediyl)bis[phenol], 4,4'-(1,2-cyclohexanediyl)bis[phenol], 4,4'-(1,3- cyclohexanediyl)bis[phenol], 4,4'-(1,4- cyclohexanediyl)bis[phenol], 4,4'-ethyllidendbis[phenol], 4,4'-(1-phenylethylidene)bis[phenol], 4,4'-propylidenbis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'-(1-methylethylidene)bis[phenol], 4,4'-(1-methylpropylidend)bis[phenol], 4,4'-(1-ethylpropylidene)bis[phenol], 4,4'-cyclohexylidendbis[phenol], 4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9,diyldi-2,1-ethandiyl)bis[phenol], 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[phenol], 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis[phenol], phenolphthalein, 4,4'-(1-methylidend)bis[2-methylphenol], 4,4'-(1-methylethylidene)bis[2-(1-methylethyl)phenol], and 2,2'-methylenebis[4-methyl-6-(1-methylethyl) phenol].
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the medium may contain triol, wherein triol may include aliphatic triol having a molecular weight of 500 or less similar such as trimethylolethan, trimethylolpropane; glycerol; 1,2,4-butanetriol; 1,2,6-hexanetriol; tris(2-hydroxyethyl)isocyanurate; hexadydro1,3,5-tris(hydroxyethyl)-s-triazine; 6-methylheptane-1,3,5-triol; polypropylene oxide triol; or polyester triol.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the medium may contain tetraol, for example, erythritol, pentaerythritol, 2,2'-dihydroxymethyl-1,3-propandiol, or 2,2'-(oxydimethylene)bis-(2-ethyl-1,3-propandiol).
In the sodium based secondary battery according to the exemplary embodiment of the present invention, at least one of the Y group of the medium may be amine.
For example, at least one of the Y group may be primary amine, secondary amine, aniline or aniline derivatives, or a N-H group which is a portion of heterocycle. For example, the medium may be polyamine and be diamine, triamine, tetramine, or higher amine oligomer.
For example, at least one of the Y group may be amine, and at least one of the additional Y group may be independently selected from a group consisting of -OH, -C(O)OH, -C(OR1)OH, -OC(R1)OH, -NHC(O)R1, -NHC(O)OR1, -C(O)NHR1, -C(S)NHR1, -OC(O)NHR1, -OC(S)NHR1, -SH, -C(O)SH, -B(OR1)OH, -P(O)a(R1)b(OR1)cOH, -OP(O)a(R1)b(OR1)cOH, -N(R1)OH, -ON(R1)H, =NOH, and =NN(R1)H.
For example, at least one of the Y group may be amine, and at least one of the additional Y group may be independently selected from a group consisting of -OH, -SH, -C(O)OH, and -C(O)NHR1. For example, the medium may be amino alcohol, amino acid, amino thiol, or amino amide.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, at least one of the Y group of the medium may be carboxylic acid or salts thereof.
For example, all of Y group present in the medium may be carboxylic salts.
For example, the medium may be biacid, triacid, or higher polyacid.
For example, n may be 1, and both of Y groups may be carboxylic acid. For example, the medium may be biacid including phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, or azelaic acid. For example, the medium may be triacid including citric acid, isocitric acid, cis- or trans-aconitic acid, propan-1,2,3-tricarboxylic acid, or trimesic acid.
For example, at least one of the Y group may be carboxylic acid or carboxylate, and at least one of the additional Y group may be independently selected from a group consisting of -OH, -C(OR1)OH, -OC(R1)OH, -NHR1, -NHC(O)R1, -NHC(O)OR1, -C(O)NHR1, -C(S)NHR1, -OC(O)NHR1, -OC(S)NHR1, -SH, -C(O)SH, -B(OR1)OH, -P(O)a(R1)b(OR1)cOH, -OP(O)a(R1)b(OR1)cOH, -N(R1)OH, -ON(R1)H, =NOH, and =NN(R1)H.
For example, at least one of the Y group may be carboxylic acid, and at least one of the additional Y group may be independently selected from a group consisting of -OH, -SH, NHR1, and -C(O)NHR1.
For example, the solvent may be amino acid and include a natural amino acid. For example, the solvent may be a peptide, wherein peptide may contain 2 to 20 amino acid residues. For example, the medium may be thiolic acid or hydroxy acid.
For example, the hydroxyl acid may be alpha-hydroxy acid. The alpha-hydroxy acid may be selected from a group consisting of glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid and mandelic acid.
For example, the hydroxyl acid may be beta-hydroxy acid. The beta-hydroxy acid be selected from a group consisting of 3-hydroxypropionic acid, DL-3-hydroxybutyric acid, D-3-hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3-hydroxyvaleric acid, L-3-hydroxyvaleric acid, and salicylic acid and salicylic acid derivatives.
For example, the hydroxy acid may be α-ω hydroxyl acid. The α-ω hydroxyl acid may be selected from a group consisting of an unsubstituted or substituted C3-20 aliphatic α-ω hydroxyl acids. For example, the α-ω hydroxy acid may be polyester oligomer ester.
In the case of at least one of the Y group is the carboxyl group, the medium may be a carboxylate salt. For example, the carboxylate salt may be a Group 1 metal salt or Group 2 metal salt.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, at least one of the Y group of the medium may be thiol. For example, at least one of the Y group may be primary thiol, and at least one of the Y group may be secondary or tertiary thiol. For example, at least one of the Y group may be thiophenol or thiophenol derivatives.
For example, the medium may be polythiol, that is, dithiol, trithiol, or, higher thiol oligomer.
For example, at least one of the Y group may be thiol, and at least one of the additional Y group may be independently selected from a group consisting of -OH, -C(O)OH, -C(OR1)OH, -OC(R1)OH, -NHR1, -NHC(O)R1, -NHC(O)OR1, -C(O)NHR1, -C(S)NHR1, -OC(O)NHR1, -OC(S)NHR1, -C(O)SH, -B(OR1)OH, -P(O)a(R1)b(OR1)cOH, -OP(O)a(R1)b(OR1)cOH, -N(R1)OH, -ON(R1)H, =NOH, and =NN(R1)H.
For example, at least one of the Y group may be thiol, and at least one of the additional Y group may be independently selected from a group consisting of -OH, -NHR1, -C(O)OH, and -C(O)NHR1.
For example, the medium may be thio alcohol, amino thiol, thiol carboxylic acid.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, at least one of the Y group may be an active NH-containing functional group. For example, a nitrogen atom of the active NH-containing functional group may be a nucleophile. For example, the active NH-containing functional group may be selected from a group consisting of C-bonded amide, N-bonded amide, O-bonded carbamate, N-bonded carbamate, urea, guanidine, amidine, hydrazone, and N- or C-bonded thioamide. For example, at least one of the Y group may be primary amide.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the catholyte solution may selectively include a material according to Chemical Formula 1 dissolved therein or further include a solvent miscibility with the material according to Chemical Formula 1. For example, the catholyte solution may further contain a material selected from a group consisting of ester, nitrile, ketone, aromatic hydrocarbon, ether, amine, and a mixture of at least two thereof.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, an operation temperature of the sodium based secondary battery may be 200℃ or less, substantially 100 to 200℃, and more substantially 100 to 150℃.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the sodium salt contained in the catholyte solution may include a sodium salt satisfying Chemical Formula 2.
[Chemical Formula 2]
Figure PCTKR2013003003-appb-I000002
R of Chemical Formula 2 is hydrogen; or a straight or branched chain C1 to C7 alkyl group.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the sodium salt contained in the catholyte solution may directly participate in charging and discharging reaction of the battery simultaneously with serving to smoothly moving sodium ions introduced through a solid electrolyte.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, at the time of charging or discharging the sodium based secondary battery, net reaction according to the following reaction formula 1 may be generated by the sodium salt.
(Reaction formula 1)
Figure PCTKR2013003003-appb-I000003
The cathode containing nickel contacts the catholyte solution. As the catholyte solution contains the sodium salt of the reaction formula 1, at the time of charging, nickel contained in the cathode may be changed into nickel compound as shown in the reaction formula 2, and at the time of discharging, the nickel compound may be changed again into nickel metal as shown in the reaction formula 3.
(Reaction formula 2) Charging reaction
Figure PCTKR2013003003-appb-I000004
(Reaction formula 3) Discharging reaction
Figure PCTKR2013003003-appb-I000005
Particularly, at the time of charging, sodium in the catholyte solution contacting the nickel metal is ionized to move to the anode through the solid electrolyte, negative ions obtained by eliminating sodium may be bonded to the nickel metal in the cathode to thereby be changed into the nickel compound. That is, sodium ion may move through the solid electrolyte during the charging to become sodium metal electrode, and (COOR)- negative ion separated from the sodium ion may be bonded to nickel losing an electron to become the nickel compound Ni(COOR)2. At the time of discharging, a reverse reaction may occur.
As describe above, the sodium salt contained in the catholyte solution may include a sodium salt according to Chemical Formula 2.
[Chemical Formula 2]
Figure PCTKR2013003003-appb-I000006
R of Chemical Formula 2 is hydrogen; or a straight or branched chain C1 to C7 alkyl group.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the sodium salt contained in the catholyte solution may be sodium acetate, sodium formate, or a mixture thereof.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, a content of the sodium salt in the catholyte solution may be 5 to 70 weight %, preferably 10 to 70 weight %, and more preferably 20 to 63 weight %.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the catholyte solution may contain sodium acetate. In this case, a content of the sodium acetate in the catholyte solution may be 5 to 70 weight %, preferably 10 to 70 weight %, and more preferably 20 to 63 weight %.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the catholyte solution may contain sodium formate. In this case, a content of the sodium formate in the catholyte solution may be 5 to 70 weight %, preferably 10 to 70 weight %, and more preferably 20 to 63 weight %.
In the case in which the content of the sodium salt in the catholyte solution is significantly low, the amount of sodium salt capable of participating in the electrochemical reaction is insufficient, such that a charging and discharging speed may be reduced and an energy capacity per unit volume may be reduced in the entire battery, and ionic conductivity in the solution is low, such that a resistance value may be increased. In the case in which the content of the sodium salt in the catholyte solution is significantly high, conductivity of the sodium ion may be reduced by a precipitate.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the cathode may include a foam, a film, a mesh, a felt, or a perforated film. As a substantial example, the cathode may include a nickel or nickel containing alloy foam, film, mesh, felt or perforated film.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the cathode (based on the discharging state) may be pure nickel; an alloy containing nickel; a laminate in which pure nickel or the nickel alloy and a conductive material are stacked; or a perforated conductor on which metal particles containing nickel are supported.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, in the case in which the cathode is the alloy containing nickel, the alloy containing nickel may be at least one of the alloy selected from nickel-copper alloy and nickel-iron alloy and substantially, be an alloy containing 0.01 to 99.9 weight% nickel.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, in the case in which the cathode is the laminate, pure nickel or the nickel alloy may contact a surface of a perforated conductor to thereby be stacked thereon in a foam, a film, a mesh, a felt, a perforated film, or a bar type or be inserted into the perforated conductor.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the cathode may be the perforated conductor having the nickel containing metal particles supported thereon or coated with the nickel containing metal particles.
As the perforated conductor, any material that has excellent conductivity and is chemically stable at the time of charging and discharging of the battery may be used. As a substantial example, the perforated conductor may be graphite, graphene, or conductive carbon including a carbon nanotube and have a foam, film, mesh, felt or perforated film type.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the cathode and the catholyte solution contact each other, which includes a shape in which the cathode including nickel is immerged in the catholyte solution. In this case, the cathode may be in a rolled state.
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the solid electrolyte having sodium ion conductivity may include a solid electrolyte generally used in the battery in order to selectively conduct the sodium ion, for example, a Na super ionic conductor (NASICON).
In the sodium based secondary battery according to the exemplary embodiment of the present invention, the NASICON may include Na-Zr-Si-O based complex oxide, Na-Zr-Si-P-O based complex oxide, Y-doped Na-Zr-Si-P-O based complex oxide, Fe-doped Na-Zr-Si-P-O based complex oxide, or a mixture thereof. A substantial example may include Y- or Fe-doped Na3Zr2Si2PO12, Y- or Fe-doped Na1+xSiXZr2P3-xO12 (1.6<x<2.4), or a mixture thereof.
The sodium based secondary battery according to the exemplary embodiment of the present invention may have a structure of a general sodium-sulfur battery having fused sodium as the anode or a structure of a sodium-nickel hydroxide battery.
FIG. 1 is a view showing a structure of a sodium based secondary battery according to an exemplary embodiment of the present invention. As shown in FIG. 1, the sodium based secondary battery according to the exemplary embodiment of the present invention may include a cylindrical metal housing 100 having a closed lower end and an opened upper end, a solid electrolyte (hereinafter solid electrolyte tube 300) sequentially positioned from an outer side of the metal housing 100 toward an inner side thereof in the metal housing 100 and having a closed lower end in a tube shape, a safety tube 410, and a wicking tube 420.
Particularly, the wicking tube 420 positioned at an innermost portion, that is, the center of the metal housing 100, may have the tube shape in which a through-hole 1 formed at a lower end thereof, and the safety tube 410 may be positioned at an outer side of the wicking tube 420 and have a structure in which the safety tube 410 encloses the wicking tube 420 while being spaced apart from the wicking tube 420 by a predetermined distance.
An anode 400 including fused sodium is provided in the wicking tube 420 and has a structure in which it fills an empty space between the wicking tube 420 and the safety tube 410 through the through-hole 1 formed at a lower portion of the wicking tube 420. A dual structure of the wicking tube 420 and the safety tube 410 is a structure capable of preventing violent reaction between cathode materials and anode materials at the time of damage of the solid electrolyte tube 300 and constantly maintaining a level of the fused sodium due to the capillary force even at the time of discharging.
The solid electrolyte tube 300 is positioned at the outer side of the safety tube 410 so as to enclose the safety tube 410 and may be the tube shaped solid electrolyte having selective permeability to the sodium ion (Na+).
A space between the solid electrolyte tube 300 enclosing the safety tube 410 and the metal housing 100 may be provided with a catholyte solution 220 containing medium according to Chemical Formula 1 and sodium salts according to Chemical Formula 2 and a cathode 210 including nickel.
That is, the sodium based secondary battery according to the exemplary embodiment of the present invention may have a concentric structure in which the wicking tube 420, the safety tube 410, the solid electrolyte tube 300, and the metal housing 100 are sequentially positioned from the inner side toward the outer side. Here, the anode 400 containing the fused sodium may be supported on the inner portion of the wicking tube 420, the catholyte solution 220 containing the sodium salt according to Chemical Formula 2 may be provided in the space between the solid electrolyte tube 300 and the metal housing 100, and the cathode 210 including nickel may be provided so as to be impregnated in the catholyte solution 220.
As shown in FIG. 1, the cathode 210 including nickel may be rolled and provided between the solid electrolyte tube 300 and the metal housing 100, but the present invention is not limited to a shape of the cathode.
In addition, the sodium based secondary battery according to the exemplary embodiment of the present invention may further include a cover 110 positioned at an upper portion of the metal housing 100 to close an inner portion of the metal housing, insulator 120 having a ring shape and positioned at an upper side of the metal housing 100 to electrically insulate the metal housing 100 form the solid electrolyte tube 300, and an electrode terminal 130 positioned at a circumference of an upper end of the metal housing 100. Further, in order to minimize evaporation of the electrolyte, immediately after manufacturing the battery, internal pressure of the battery closed by the cover 110 may be 15psi or more, and the anode including the nickel impregnated in the catholyte solution may be electrically connected to the metal housing 100. Furthermore, an anode current collector may be input through a through-hole of the cover 110 so as to be impregnated by a predetermined area in the fused sodium anode supported on the inner portion of the wicking tube 420.
FIG. 2 is a view obtained by measuring charge and discharge characteristics of a sodium secondary battery manufactured using nickel as a cathode, metal sodium as an anode, and glycerol in which 20 weight% of sodium formate is dissolved as a catholyte solution. In detail, after 55mg of nickel mesh was cut in a circular shape, the nickel mesh was used as the cathode and connected to a platinum line used as a current collector. In addition, 635mg of the solution (catholyte solution) in which 20 weight% of sodium formate is dissolved in glycerol was injected. NaSICON having a thickness of 1mm and an area of 2cm2 was used as a solid electrolyte, and 100mg of the sodium metal was injected into the anode in an opposite side of the NaSICON solid electrolyte, thereby configuring the battery. The charge and discharge characteristics shown in FIG. 2 were results obtained by heating the secondary battery manufactured as described above to 110℃ and then flowing 5mA of current to charge and discharge the secondary battery for 4 hours, respectively.
Hereinabove, although the present invention is described by specific matters, exemplary embodiments, and drawings, they are provided only for assisting in the entire understanding of the present invention. Therefore, the present invention is not limited to the exemplary embodiments. Various modifications and changes may be made by those skilled in the art to which the present invention pertains from this description.
Therefore, the spirit of the present invention should not be limited to the above-described exemplary embodiments, and the following claims as well as all modified equally or equivalently to the claims are intended to fall within the scope and spirit of the invention.

Claims (12)

  1. A sodium based secondary battery comprising:
    an anode containing sodium;
    a catholyte solution containing a sodium salt and a medium defined by the following Chemical Formula 1;
    a cathode contacting the catholyte solution; and
    a solid electrolyte provided between the anode and the catholyte solution and having sodium ion conductivity.
    (Chemical Formula 1)
    Y-A-(Y)n
    (where the respective Ys are the same as or different from each other and are independently selected from a group consisting of -OH, -C(O)OH, -C(OR1)OH, -OC(R1)OH, -NHR1, -NHC(O)R1, -NHC=NR1, -NR1C=NH, -NR1C(NR1 2)=NH, -NHC(NR1 2)=NR1, -NHC(O)OR1, -NHC(O)NR1 2, -C(O)NHR1, -C(S)NHR1, -OC(O)NHR1, -OC(S)NHR1, -SH, -C(O)SH, -B(OR1)OH, -P(O)a(R1)b(OR1)c(O)dH, -OP(O)a(R1)b(OR1)c(O)dH, -N(R1)OH, -ON(R1)H, =NOH, and =NN(R1)H, wherein R1 each independently is -H or a substituted or unsubstituted radical selected from a group consisting of C1-20 aliphatic, C1-20 hetero aliphatic, 3- to 12-membered heterocyclic and 6- to 12-membered aryl, a and b are each independently 0 or 1, c each independently is 0, 1, or 2, d each independently is 0 or 1, the sum of a, b, and c is 1 or 2, an acidic hydrogen atom bonded to one of the Y is substituted by a metal atom or organic positive ion, -A- is covalent bonding or a multivalent residue, and n is an integer of 1 to 10).
  2. The sodium based secondary battery of claim 1, wherein the respective Ys in Chemical Formula 1 are independently selected from a group consisting of -OH and -C(O)OH.
  3. The sodium based secondary battery of claim 1, wherein -A- in Chemical Formula is a substituted or unsubstituted radical selected from a group consisting of C2-30 aliphatic, C2-30 hetero aliphatic, 6- to 12-membered aryl, 3- to 12-membered heterocyclic, 5-12-membered heteroaryl, polyolefin, polyester, polyether, polycarbonate, polyoxymethylene, and a mixture of at least two thereof.
  4. The sodium based secondary battery of claim 1, wherein n in Chemical Formula 1 is 1 to 4.
  5. The sodium based secondary battery of claim 1, wherein the medium includes polyhydric alcohol or hydroxy acid.
  6. The sodium based secondary battery of claim 1, wherein the medium includes one or at least two of the materials selected from a group consisting of 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-propane-1 ,3-diol, 2-butyl-2-ethylpropane-1,3-diol, 1,5-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 2,2,4,4-tetramethylcyclobutane-1,3-diol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediethanol, glycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, and poly propylene glycol.
  7. The sodium based secondary battery of claim 1, wherein the medium includes one or at least two of materials selected from a group consisting of 4,4'-(1-methylethyliden)bis[cyclohexanol], 2,2'-methylenebis[phenol], 4,4 '-methylenebis[phenol], 4,4'-(phenylmethylene)bis[phenol], 4,4'-(diphenylmethylene)bis[phenol], 4,4'-(1,2-ethanediyl)bis[phenol], 4,4'-(1,2-cyclohexanediyl)bis[phenol], 4,4'-(1,3- cyclohexanediyl)bis[phenol], 4,4'-(1,4- cyclohexanediyl)bis[phenol], 4,4'-ethyllidendbis[phenol], 4,4'-(1-phenylethylidene)bis[phenol], 4,4'-propylidenbis[phenol], 4,4'-cyclohexylidenebis[phenol], 4,4'-(1-methylethylidene)bis[phenol], 4,4'-(1-methylpropylidend)bis[phenol], 4,4'-(1-ethylpropylidene)bis[phenol], 4,4'-cyclohexylidendbis[phenol], 4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9,diyldi-2,1-ethandiyl)bis[phenol], 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bis[phenol], 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis[phenol], phenolphthalein, 4,4'-(1-methylidend)bis[2-methylphenol], 4,4'-(1-methylethylidene)bis[2-(1-methylethyl)phenol], and 2,2'-methylenebis[4-methyl-6-(1-methylethyl) phenol].
  8. The sodium based secondary battery of claim 1, wherein the medium includes one or at least two of materials selected from a group consisting of glycolic acid, DL-lactic acid, D-lactic acid, L-lactic acid, citric acid, mandelic acid, 3-hydroxypropionic acid, DL-3-hydroxybutyric acid, D-3-hydroxybutyric acid, L-3-hydroxybutyric acid, DL-3-hydroxyvaleric acid, D-3-hydroxyvaleric acid, L-3-hydroxyvaleric acid, salicylic acid, salicylic acid derivatives, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, succinic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.
  9. The sodium based secondary battery of claim 1, wherein the sodium salt includes an organic sodium salt defined by the following Chemical Formula 2.
    (Chemical Formula 2)
    Figure PCTKR2013003003-appb-I000007
    (R in Chemical Formula 2 is hydrogen; or a straight or branched chain C1 to C7 alkyl group).
  10. The sodium based secondary battery of any one of claims 1 to 9, wherein the anode includes metallic sodium, and the cathode includes nickel.
  11. The sodium based secondary battery of any one of claims 1 to 9, wherein the catholyte solution includes 5 to 70 weight % sodium salt.
  12. The sodium based secondary battery of any one of claims 1 to 9, wherein it is operated at a temperature of 100 to 200℃.
PCT/KR2013/003003 2012-04-10 2013-04-10 Sodium secondary battery WO2013154349A1 (en)

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WO2016089902A1 (en) * 2014-12-04 2016-06-09 Ceramatec, Inc. Sodium-halogen secondary cell
US10020543B2 (en) 2010-11-05 2018-07-10 Field Upgrading Usa, Inc. Low temperature battery with molten sodium-FSA electrolyte
US10056651B2 (en) 2010-11-05 2018-08-21 Field Upgrading Usa, Inc. Low temperature secondary cell with sodium intercalation electrode
US10224577B2 (en) 2011-11-07 2019-03-05 Field Upgrading Usa, Inc. Battery charge transfer mechanisms
US10320033B2 (en) 2008-01-30 2019-06-11 Enlighten Innovations Inc. Alkali metal ion battery using alkali metal conductive ceramic separator
US10854929B2 (en) 2012-09-06 2020-12-01 Field Upgrading Usa, Inc. Sodium-halogen secondary cell

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US20110104526A1 (en) * 2009-11-05 2011-05-05 Chett Boxley Solid-state sodium-based secondary cell having a sodium ion conductive ceramic separator
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US10320033B2 (en) 2008-01-30 2019-06-11 Enlighten Innovations Inc. Alkali metal ion battery using alkali metal conductive ceramic separator
US10020543B2 (en) 2010-11-05 2018-07-10 Field Upgrading Usa, Inc. Low temperature battery with molten sodium-FSA electrolyte
US10056651B2 (en) 2010-11-05 2018-08-21 Field Upgrading Usa, Inc. Low temperature secondary cell with sodium intercalation electrode
US10224577B2 (en) 2011-11-07 2019-03-05 Field Upgrading Usa, Inc. Battery charge transfer mechanisms
US10854929B2 (en) 2012-09-06 2020-12-01 Field Upgrading Usa, Inc. Sodium-halogen secondary cell
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