CN103098286A - Battery assembly - Google Patents

Battery assembly Download PDF

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Publication number
CN103098286A
CN103098286A CN2011800430644A CN201180043064A CN103098286A CN 103098286 A CN103098286 A CN 103098286A CN 2011800430644 A CN2011800430644 A CN 2011800430644A CN 201180043064 A CN201180043064 A CN 201180043064A CN 103098286 A CN103098286 A CN 103098286A
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CN
China
Prior art keywords
battery pack
methyl
discharge
charging
battery
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CN2011800430644A
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Chinese (zh)
Inventor
中山哲理
影浦淳一
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of CN103098286A publication Critical patent/CN103098286A/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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/42—Grouping of primary cells into batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Mounting, Suspending (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Provided is a battery assembly in which it is difficult for degrading of battery performance due to over-discharging to occur even without use of a protective circuit. The present invention is a battery assembly in which a plurality of single battery cells are connected to each other, wherein these single battery cells are sodium ion secondary batteries having a positive electrode that include a positive electrode active material capable of sodium ion doping and undoping, a negative electrode, and an electrolyte.

Description

Battery pack
Technical field
The present invention relates to a kind of battery pack that a plurality of monocells are connected and/or are formed in parallel.
Background technology
In the middle of rechargeable nonaqueous electrolytic battery, lithium rechargeable battery is usually to use LiMO in positive pole 2Oxides such as (M are the transition metal such as Co, Mn, Ni), use the secondary cell of the compound of the electronegative potentials such as material with carbon element or lithium in negative pole.In recent years,, use a plurality of monocells series connection and/or the battery pack that is formed in parallel with power supply etc. as the power supply of electric motor car, electric power equalization, particularly, in order to obtain high voltage, high power capacity, mostly utilize lithium secondary battery as this kind secondary cell.The monocell that consists of battery pack has the various patterns such as cylinder type, square, lamination-type.
But, commercially available lithium rechargeable battery (monocell) uses in the scope of 3～4V usually in order not cause degradation of cell performance, yet when discharging and recharging, in case be charged to set-point above (overcharging) or discharge into set-point following (overdischarge), the characteristic of lithium rechargeable battery will be significantly deteriorated.
Particularly when making cell voltage compare decline with given lower voltage limit because of overdischarge, will produce the stripping of copper of the collector body of negative pole, make and insert lithium ion too much with the current collection reduction of negative electrode active material, in the positive pole and make anodal deteriorated or lithium and as the aluminium alloying of the collector body of positive electrode, thereby have the problem of volume lowering.
In the situation that connect a plurality of lithium rechargeable battery (monocell) and charge or discharge, because of capacity difference or the internal resistance of each battery poor, the balance of cell voltage is damaged, even the cell voltage of battery pack integral body is in given range, also have the situation that produces the monocell that reaches overcharge condition or over-discharge state in the part of the monocell that consists of battery pack.
For example, in the situation that to being that the battery pack of 3 of monocell series connection of the lithium rechargeable battery of 3.0V is discharged with lower voltage limit, so that whole cell voltage is that the mode of voltage of 9.0V is with battery power discharge.At this moment, in the situation that the capacity of above-mentioned 3 monocells is different, has certain monocell and reach that 3.0V is following, other certain monocell reaches the above situation of 3.0V.The monocell that reaches the following voltage of 3.0V is overdischarge, and battery performance reduces significantly.
The problem of the overdischarge in this kind battery pack, known in battery pack, usually except above-mentioned monocell, also arrange the temperature that detects each monocell temperature sensor, detect the potentiometer etc. of the voltage of each monocell.In addition, will utilize the detected temperature of these temperature sensors or potentiometer or voltage to offer control device via holding wire, and utilize control device to control battery pack (for example with reference to No. 3773350 communique of Japan's special permission).
Above-mentioned each transducer and control device be not only for control battery pack discharge and recharge end condition and also for fear of the overcharging of the monocell that consists of battery pack, overdischarge and essential electronic circuit component.
The prior art document
Patent documentation
Patent documentation 1: No. 3773350 communique of Japan's special permission
The summary of invention
Invent problem to be solved
But if above-mentioned each transducer and control device are set in battery pack, the volume of battery pack integral body will become greatly, causes the problem of the energy density reduction of battery pack.Particularly become many in the situation that consist of the number of the monocell of battery pack, also might cause the increasing considerably of cost of battery pack.
Be used for Way to solve the problem
Under this situation, the object of the invention is to, even a kind of deteriorated battery pack of not using protective circuit also to be not easy to cause the battery performance that is caused by overdischarge is provided.
The invention of this part is as follows.
＜1〉a kind of battery pack is that a plurality of monocells are interconnected the battery pack that forms, and described monocell is to have to comprise positive pole, negative pole and the electrolytical sodium ion secondary battery that can adulterate, remove the positive active material of sodium contaminated ion.
＜2〉according to described＜1〉record battery pack, wherein, described positive active material is the sodium transistion metal compound that can adulterate, go the sodium contaminated ion.
＜3〉according to described＜2〉the middle battery pack of putting down in writing, wherein, described sodium transistion metal compound is with NaM 1O 2(M 1The transition metal of expression more than a kind.) expression oxide.
＜4〉according to described＜1 〉～＜3 any one in the battery pack put down in writing, wherein, comprise at least one parallel connection.
The effect of invention
According to the present invention, even a kind of deteriorated battery pack of not using protective circuit also to be not easy to cause the battery performance that is caused by overdischarge can be provided.
Embodiment
Battery pack of the present invention is that the monocell that will be made of sodium ion secondary battery (is designated hereinafter simply as " monocell ".) a plurality of batteries that form of connection.A plurality of monocells are electrically connected to mutually.
Below, the monocell that becomes the component unit of battery pack of the present invention must have the positive pole that can adulterate, remove the sodium contaminated ion, negative pole and the electrolyte that can adulterate, go the sodium contaminated ion, usually has the barrier film that separates positive pole, negative pole.
Below, the inscape of monocell is described.
(1) positive pole
Positive pole is made of positive electrode collector and the anode mixture that supports on positive electrode collector.Electric conducting material, binding agent that anode mixture comprises positive active material and uses as required.
As positive active material, so long as TiS 2Sulfides, Fe 3O 4Deng oxide, Fe 2(SO 4) 3Deng sulfate, FePO 4Deng phosphate, FeF 3The material of sodium contaminated ion that can adulterate, go in fluoride etc. and so on gets final product, yet is particularly preferably the sodium transistion metal compound as the compound of sodium and transition metal.And the transition metal in the sodium transistion metal compound can at random be selected can enumerate Ti, V, Cr, Mn, Fe, Co, Ni and Cu etc. specifically more than a kind.
As the sodium transistion metal compound, for example can enumerate:
With Na xM 1O yOxide (the M of expression 1The transition metal of expression more than a kind, x, y are the values that satisfies 0.4＜x＜2,1.9＜y＜2.1.)；
Na 6Fe 2Si 12O 30And Na 2Fe 5Si 12O 30Deng with Na bM 2 cSi 12O 30Silicate (the M of expression 2The transition metal of expression more than a kind, b, c are the values that satisfies 2≤b≤6,2≤c≤5.)；
Na 2Fe 2Si 6O 18And Na 2MnFeSi 6O 18Deng with Na dM 3 eSi 6O 18Silicate (the M of expression 3The transition metal of expression more than a kind, d, e are the values that satisfies 3≤d≤6,1≤e≤2.)；
Na 2FeSiO 6Deng with Na fM 4 gSi 2O 6Silicate (the M of expression 4Expression is selected from the element more than a kind in transition metal, Mg and Al, and f, g are the values that satisfies 1≤f≤2,1≤g≤2.)；
NaFePO 4, NaMnPO 4, NaNiPO 4Deng with NaM 6 aPO 4Phosphate (the M of expression 6The transition metal of expression more than a kind.)；
Na 3Fe 2(PO 4) 3Deng phosphate;
NaFeSO 4The sulfate such as F;
NaFeBO 4, Na 3Fe 2(BO 4) 3Deng borate;
Na 3FeF 6And Na 2MnF 6Deng with Na hM 5F 6Fluoride (the M of expression 5The transition metal of expression more than a kind, h are the values that satisfies 2≤h≤3.) etc., they can use a kind or be mixed with two or more.
Wherein, be preferably with NaM 1O 2(M 1The transition metal of expression more than a kind.) expression oxide.As its suitable concrete example, can enumerate and have α-NaFeO 2The NaMnO of the structure of type 2, NaNiO 2And NaCoO 2And NaFe 1-p-qMn pNi qO 2(p, q are the values that satisfies lower relation of plane.0≤p+q≤1,0≤p≤1,0≤q≤1) oxide such as.
In above-mentioned sodium transistion metal compound, also can in the scope of the effect of damaging invention, the part of above-mentioned transition metal be replaced with the metallic element beyond above-mentioned transition metal not obviously.By replacing, can be improved the situation of the characteristic of battery pack of the present invention.As the metal beyond above-mentioned transition metal, can enumerate the metallic elements such as Li, K, Ag, Mg, Ca, Sr, Ba, Al, Ga, In, Zn, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb and Lu.
As positive electrode collector, so long as conductivity is high and material that be easy to be processed as film gets final product, can use the metals such as Al, Ni, stainless steel, Cu etc.As the shape of positive electrode collector, belong to paper tinsel shape, tabular, mesh-shape, netted, lath-shaped such as enumerating, punch metal is tabular or the shape of embossing shape or with the shape of their combinations (such as the mesh-shape flat board etc.) etc.
Material with carbon element can be used as described electric conducting material, the fibrous carbon materials such as powdered graphite, carbon black, carbon nano-tube etc. can be enumerated as material with carbon element.
＜binding agent 〉
As binding agent used in described positive pole, for example can enumerate the polymer of fluorine compounds.As fluorine compounds, for example can enumerate fluorinated alkyl (carbon number 1～18) (methyl) acrylate, perfluoroalkyl (methyl) acrylate [for example perfluor dodecyl (methyl) acrylate, perfluor n-octyl (methyl) acrylate, perfluor normal-butyl (methyl) acrylate];
Perfluoroalkyl substituted alkyl (methyl) acrylate [for example perfluoro hexyl ethyl (methyl) acrylate and perfluoro capryl ethyl (methyl) acrylate];
Perfluor oxygen base alkyl (methyl) acrylate [for example perfluor dodecyl oxygen base ethyl (methyl) acrylate and perfluor decyl oxygen base ethyl (methyl) acrylate];
Fluorinated alkyl (carbon number 1～18) crotonates;
Fluorinated alkyl (carbon number 1～18) malate and fumarate;
Fluorinated alkyl (carbon number 1～18) itaconate and fluorinated alkyl substituted olefine (carbon number 2～10 left and right, number of fluorine atoms 1～17 left and right) [for example perfluoro hexyl ethene, tetrafluoroethene, trifluoro-ethylene, Kynoar (the following PVdF that sometimes is called.) and hexafluoropropylene].
As the example beyond the polymer of the fluorine compounds of binding agent, can enumerate the addition polymer of the monomer that comprises the two keys of ethylenic that does not contain fluorine atom.As this monomer, for example can enumerate (ring) alkyl (carbon number 1～22) (methyl) acrylate [for example (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) cyclohexyl acrylate, (methyl) 2-EHA, (methyl) isodecyl acrylate, (methyl) lauryl acrylate and (methyl) acrylic acid octyl group ester in the last of the ten Heavenly stems];
(methyl) acrylate [for example (methyl) benzyl acrylate and (methyl) phenylethyl] that contains aromatic rings;
List (methyl) acrylate of alkylene glycol or two alkylene glycol (carbon number of alkylidene is 2～4) [for example (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate and diglycol monotertiary (methyl) acrylate];
Single (methyl) acrylate of (gathering) glycerol (degree of polymerization 1～4);
(methyl) acrylic ester monomers such as multifunctional (methyl) acrylate [for example (gathering) ethylene glycol (degree of polymerization 1～100) two (methyl) acrylate, (gathering) propylene glycol (degree of polymerization 1～100) two (methyl) acrylate, 2, two (4-ethoxy phenyl) propane two (methyl) acrylate of 2-and trimethylolpropane tris (methyl) acrylate];
(methyl) acrylamide monomers such as (methyl) acrylamide, (methyl) acrylamide derivative [such as N-methylol (methyl) acrylamide and DAAM];
(methyl) acrylonitrile, (methyl) 2 cyanoethyl acrylate and 2-cyano ethyl acrylamide etc. contain the monomer of cyano group;
The styrenic monomers such as the styrene derivative of styrene and carbon number 7～18 [such as AMS, vinyltoluene, p-hydroxy styrenes and divinylbenzene];
The diene monomers such as the alkane diene of carbon number 4～12 [such as butadiene, isoprene and chlorobutadiene];
Carboxylic acid (carbon number 2～12) vinyl esters [for example vinyl acetate, propionate, vinyl butyrate and sad vinyl acetate];
The alkenyl esters such as carboxylic acid (carbon number 2～12) (methyl) allyl ester [such as acetic acid (methyl) allyl ester, propionic acid (methyl) allyl ester and sad (methyl) allyl ester] are monomer;
(methyl) glycidyl acrylate, (methyl) allyl glycidyl ether etc. contain the monomer of epoxy radicals;
The monoene hydro carbons of monoolefine (carbon number 2～12) [for example ethene, propylene, 1-butylene, 1-octene and 1-laurylene];
The monomer that contains chlorine, bromine or iodine atom;
Vinyl chloride, vinylidene chloride etc. contain the monomer of the halogen atom beyond fluorine;
Acrylic acid, methacrylic acid etc. (methyl) acrylic acid;
Butadiene, isoprene etc. contain the monomer of conjugated double bond.
In addition, as addition polymer, such as can be also the copolymers such as EVAc, styrene-butadiene-copolymer or ethylene propylene copolymer.In addition, the carboxylic acid vinyl ester polymer also can be by partially or even wholly saponification.Binding agent can be also the copolymer of fluorine compounds and the monomer that comprises the two keys of ethylenic that does not contain fluorine atom.
As other illustration of binding agent, can enumerate polysaccharide and the derivatives thereof such as starch, methylcellulose, carboxymethyl cellulose, CMC, hydroxyethylcellulose, hydroxypropyl cellulose, carboxymethyl hydroxyethyl cellulose, NC Nitroncellulose; Phenolic resins; Melamine resin; Polyurethane resin; Urea resin; Polyamide; Polyimide resin; Polyamide-imide resin; Petroleum asphalt; Coal tar pitch.
As binding agent, the polymer of fluorine compounds particularly preferably is especially particularly preferably as the polytetrafluoroethylene of the polymer of tetrafluoroethene.In addition, also can use above-mentioned multiple binding agent as binding agent.In addition, in the operation of the coating on positive electrode collector, in order to make the coating on the positive electrode collector easy, also can use thickener or fall thick dose.
As support the method for anode mixture in positive electrode collector, can enumerate the method for extrusion forming; Or use the in addition paste and be coated on positive electrode collector, suppress after drying etc. and the method for set such as organic solvent.As the method that anode mixture is coated with on the positive electrode collector, such as enumerating slit die rubbing method, silk screen rubbing method, excellent rubbing method etc.
(2) negative pole
As long as negative pole has the material that can adulterate, remove the sodium contaminated ion under the current potential lower than positive pole, can enumerate the cathode agent that to contain negative material and be supported on the electrode that forms on negative electrode collector or the electrode that is consisted of separately by negative material.As negative material, can enumerate the doping that belongs to material with carbon element, chalcogen compound (oxide, sulfide etc.), nitride, metal or alloy and can carry out sodium ion under the current potential lower than positive pole, remove the material that adulterates.In addition, these negative materials also can mix use.
As follows for described negative material illustration.As described material with carbon element, specifically, can enumerate in the middle of the graphite such as native graphite, Delanium, coke class, carbon black, thermally decomposed carbon class, carbon fiber, the organic high molecular compound sintered body etc., can carry out under the current potential lower than positive pole sodium ion doping, remove the material that adulterates.These material with carbon elements, oxide, sulfide, nitride also may be used, can be crystalline or amorphous any one.In addition, these material with carbon elements, oxide, sulfide, nitride mainly support on negative electrode collector, use as negative pole.
As the shape of material with carbon element, such as any one of agglomerate etc. of fibrous or micropowder that can be spherical, the graphitized carbon fibre and so on of laminar, the meso carbon micro beads and so on native graphite.
In addition, as the doping that can carry out sodium ion under the current potential lower than positive pole, remove the described metal that adulterates, specifically, can enumerate sodium metal, silicon metal, tin metal.In addition, as the doping that can carry out sodium ion under the current potential lower than positive pole, remove the described alloy that adulterates, except the ashbury metals such as the silicon alloys such as the sodium alloys such as Na-Al, Na-Ni, Na-Si, Si-Zn, Sn-Mn, Sn-Co, Sn-Ni, Sn-Cu, Sn-La, can also enumerate Cu 2Sb, La 3Ni 2Sn 7Deng alloy.These metals, alloy mainly use (for example using with the paper tinsel shape) as negative pole individually.
Described cathode agent also can contain binding agent as required.As binding agent, can enumerate thermoplastic resin, specifically, can enumerate binder phase used in PVdF, thermoplastic polyimide, carboxymethyl cellulose, polyethylene, polypropylene etc. and positive pole with material.In the situation that electrolyte does not contain ethylene carbonate described later, if use the cathode agent that contains the polymerized thylene carbonate ethyl ester, can be improved the situation that recycles characteristic and heavy-current discharge characteristic of the battery of gained.
As negative electrode collector, can enumerate Cu, Ni, stainless steel etc., from be difficult to form the aspect of alloy with sodium, the aspect that is easy to be processed as film is considered, preferred Cu.
As the shape of negative electrode collector, such as can enumerate paper tinsel shape, tabular, mesh-shape, netted, lath-shaped, punch metal is tabular or the shape of embossing shape or with the shape of their combinations (such as the mesh-shape flat board etc.) etc.Also can form on negative electrode collector surface by etch processes obtain concavo-convex.
(3) electrolyte
Below, electrolyte is described.As electrolyte, can enumerate NaClO 4, NaPF 6, NaAsF 6, NaSbF 6, NaBF 4, NaCF 3SO 3, NaN (SO 2CF 3) 2, lower aliphatic carboxylic acid sodium salt, NaAlCl 4Deng, also can use their mixture more than 2 kinds.In the middle of them, preferably use to comprise to be selected from the NaPF that contains fluorine 6, NaAsF 6, NaSbF 6, NaBF 4, NaCF 3SO 3And NaN (SO 2CF 3) 2In the material of at least a kind.In addition, in the present invention, electrolyte preferably uses as the state (aqueous) that is dissolved in organic solvent, namely uses as nonaqueous electrolytic solution.
As the organic solvent in nonaqueous electrolytic solution, for example can use propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, isobutyl carbonate propyl group methyl esters, vinylene carbonate, 4-Trifluoromethyl-1,3-dioxolan-2-one, 1, the carbonates such as 2-two (methoxycarbonyl oxygen base) ethane; 1,2-dimethoxy-ethane, 1,3-dimethoxy propane, five fluoropropyl methyl ethers, 2,2,3, the ethers such as 3-tetrafluoro propyl group difluoro methyl ether, oxolane, 2-methyltetrahydrofuran; The ester classes such as methyl formate, methyl acetate, gamma-butyrolacton; The nitrile such as acetonitrile, butyronitrile; The amide-type such as DMF, DMA; 3-methyl-carbamatess such as 2-oxazolidone; Sulfolane, methyl-sulfoxide, 1, the sulfur-containing compounds such as 3-the third sultone; Or imported again the material of fluoro substituents in above-mentioned organic solvent.As organic solvent, also mixing more than two kinds in the middle of them can be used.
Electrolytical concentration in nonaqueous electrolytic solution is generally left and right, 0.1 mole/L～2 mole/L, is preferably left and right, 0.3 mole/L～1.5 mole/L.
In addition, in the present invention, electrolyte both can be used as the state that keeps described nonaqueous electrolytic solution in macromolecular compound, namely used as gel-like electrolyte, also can be used as the solid shape, namely used as solid electrolyte.As solid electrolyte, maintain described electrolytical organic system solid electrolyte such as in the macromolecular compound more than at least a in can using macromolecular compound in poly(ethylene oxide) system, comprising polysiloxane chain or polyoxyalkylene chain etc.In addition, also can use Na 2S-SiS 2, Na 2S-GeS 2, NaTi 2(PO 4) 3, NaFe 2(PO 4) 3, Na 2(SO 4) 3, Fe 2(SO 4) 2(PO 4), Fe 2(MoO 4) 3, beta-alumina, " aluminium oxide, NASICON etc. are inorganic is solid electrolyte to β.
(4) barrier film
As barrier film, such as can use consisted of by materials such as the vistanexes such as polyethylene, polypropylene, fluororesin, nitrogenous aromatic polymers, have porous membrane, nonwoven fabrics, the material of the form such as weave cotton cloth, in addition, also can make barrier film with the described material more than 2 kinds, can also described material is stacked.As barrier film, such as the barrier film that can enumerate record in TOHKEMY 2000-30686 communique, Japanese kokai publication hei 10-324758 communique etc.For the thickness of barrier film, consider from the volume energy density that improves battery, the aspect that reduces internal resistance, as long as can guarantee mechanical strength, get over Bao Yuehao.The thickness of barrier film is generally about 5～200 μ m, is preferably about 5～40 μ m.
Barrier film preferably has the porous membrane that contains thermoplastic resin.In sodium rechargeable battery, as a rule, former because of the short circuit between positive pole-negative pole etc. thereby when flowing through abnormal current in battery, blocking-up electric current and to stop super-high-current to flow through (shutoff) very important.So, for barrier film, requirement is in the situation that surpass common serviceability temperature, shutoff at low temperatures as much as possible (in the situation that barrier film has the porous membrane that contains thermoplastic resin, the minute aperture of porous membrane is inaccessible), require in addition to have no progeny in the pass, even the temperature in battery is elevated to the high temperature of certain degree, can because of this temperature rupture of membranes, not keep the state of shutoff yet, in other words, require thermal endurance high.
By use comprise will contain the heat-resisting porous layer of heat stable resin and the barrier film of the stacked stacked porous membrane that forms of porous membrane that contains thermoplastic resin as barrier film, can further prevent hot rupture of membranes.Here, heat-resisting porous layer also can be laminated in the two sides of porous membrane.
Monocell can be made as shown below, that is, in being accommodated in by electrode group stacked, that above-mentioned positive pole, barrier film and the negative pole of reeling get the container such as battery can after, infiltrate and make by containing the electrolyte that electrolytical organic solvent consists of.
As the shape of described electrode group, the cross section such as can enumerate this electrode group along the direction cutting vertical with the axle of reeling the time for circle, ellipse, rectangle, removed the shape the rectangle etc. at angle.In addition, as the shape of battery, such as enumerating the shapes such as paper mold, coin shape, cylinder type, square.
(battery pack)
Battery pack of the present invention is to be formed by connecting as component unit and with a plurality of monocells with above-mentioned monocell, comprise only be connected in series that monocell forms, only connect in parallel that monocell forms, combined serial and connect with being connected the whole circumstances that monocell forms.This monocell is cylinder type, square, cascade type etc., and form is varied.
For more be difficult to cause by overdischarge cause deteriorated, battery pack of the present invention preferably includes at least one parallel connection.In addition, more preferably comprise at least one parallel connection, and be between the battery pack of relation in parallel, the number of monocell equates.
(connection)
In connection between each monocell, can use metal busbar, lead-in wire, ring, the nuts etc. such as copper, nickel, aluminium or their alloy, even and the metal beyond them so long as can realize that the metal of the present application purpose gets final product, therefore is not particularly limited.
In addition, as its welding method, can use spot welding or ultrasonic vibration welding etc.
(configuration)
In battery pack of the present invention, the battery pack that a plurality of monocells of serial or parallel connection form is incorporated in housing.
From the lightness of battery pack and guarantee that the viewpoint of intensity considers, above-mentioned housing preferably is made of synthetic resin such as polypropylene.
Above-mentioned housing preferably has air intake and air outlet.By air intake and air outlet are set, can promote the emitting of heat of battery pack inside, avoid the abnormal temperature of battery pack to raise.In addition, by using cooling fan, promote the circulation of the air of battery pack inside, can further reduce the overheated of battery pack.
In addition, also can be by utilizing the cooling devices such as cooling fan, the heat of the external packing box of battery pack is emitted, and indirectly carry out the heat release of battery pack inside.
(circuit member)
Also can arrange as required in battery pack of the present invention the temperature that detects each monocell temperature sensor, detect the potentiometer etc. of the voltage of each monocell.In addition, also can have the control device of controlling battery pack based on the information of utilizing the detected temperature of these temperature sensors or potentiometer or voltage.
Above-mentioned battery pack also can have the control device that prevents the overcharging of battery, overdischarge.The overcharging of battery, overdischarge can be prevented by having this control device, will having, the effect in the life-span of battery can be improved.And, not necessarily need overdischarge to prevent locking apparatus in battery pack of the present invention.
Embodiment
Below, the present invention will be described in more detail to utilize embodiment, however the present invention is only otherwise change its purport, is not limited to following embodiment.
Comparative example 1
(1) anodal making
Purity 99%), cobalt oxide (II, III) (Co use lithium hydroxide (LiOH: Wako Pure Chemical Industries, Ltd.'s system: purity is more than 95%), nickel oxide (II) (NiO: Co., Ltd.'s high-purity chemical institute system: 3O 4: Co., Ltd.'s high-purity chemical institute system: purity is more than 90%) so that Li: Ni: the mol ratio of Co was the mode weighing of 1: 0.8: 0.2, obtained raw mix with dry ball mixing 4 hours.The raw mix of gained is filled in alumina boat, kept 6 hours under 750 ℃ by using electric furnace to heat in oxygen atmosphere, obtain positive active material A 1In addition, use acetylene black as conductive agent (electrochemical industry Co., Ltd. system), as the PVdF (Kureha of Co., Ltd. system) of binding agent, to reach positive active material A 1: conductive agent: the mode of the composition of binding agent=85: 10: 5 (weight ratio) is weighing positive active material A respectively 1, conductive agent and binding agent, obtain anode mixture.At first with positive active material A 1Mix fully in agate mortar with conductive agent, add in right amount METHYLPYRROLIDONE (NMP: Tokyo HuaCheng Industry Co., Ltd's system), then add PVdF, then mix, obtain slurries in this mixture.Use applicator to be coated on aluminium foil as the thick 40 μ m of positive electrode collector with the thickness of 100 μ m in the slurries of gained, put it in drying machine, dry fully by when removing NMP, and obtain positive plate.Use roll squeezer to carry out fixedization of coating layer this positive plate.In addition, utilize ultrasonic welding machine welding Al paper tinsel, it as contact conductor, is obtained anodal B 1
(2) making of negative pole
As negative material, use native graphite and Delanium, with its with as the PVdF (Kureha of Co., Ltd. system) of binding agent so that native graphite: Delanium: the weight ratio of adhesive is the mode weighing of the ratio of 58.8: 39.2: 2, obtain cathode agent, binding agent is dissolved in as after in the NMP of solvent, adds material with carbon element C 1After slurried materials'use applicator is coated on Copper Foil as the thick 10 μ m of negative electrode collector with the thickness of 100 μ m, put it in drying machine, dry fully by when removing NMP, and obtain negative plate.Use roll squeezer to carry out fixedization of coating layer this negative plate.In addition, with ultrasonic welding machine welding Ni paper tinsel, it as contact conductor, is obtained negative pole D 1
(3) making of monocell
A side that is coated with anode mixture is placed anodal B up 1, stacked polypropylene porous film as barrier film (thick 20 μ m), will be coated with the negative pole D that a side of cathode agent is placed down 1, obtain the electrode group.The electrode group is inserted in the battery case (lamination Al bag) that the film by the thickness of 10 μ m consists of.
By ethylene carbonate and dimethyl carbonate etc. in the capacity mixed solvent with the ratio dissolving LiPF of 1.5mol/L 6And the preparation nonaqueous electrolytic solution.By injecting described nonaqueous electrolytic solution in the battery case after described electrode insertion group, carry out the vacuum lamination sealing, and produce sodium ion secondary battery E 1And, carry out in the glove box that is assembled in argon gas atmosphere of test cell.So that the charging capacity of the negative pole of per unit area is that more than 1, the mode addition weight below 2 makes up with respect to the charging capacity of the positive pole of per unit area.
Here said " charging capacity of the positive pole of per unit area " refers to, with the current value of 0.1C with constant current charge to 4.2V (with respect to lithium to electrode), according to this charging, calculate the charging capacity of per unit area.Said " charging capacity of the negative pole of per unit area " refers in addition, with the current value of 0.05C with constant current charge to 0.5mV (with respect to lithium to electrode), according to this charging, calculate the charging capacity of per unit area.
(4) making of battery pack
Make and lithium rechargeable battery E 1Identical battery E 2, E 3, E 4, E 5, all in parallel, obtain battery pack F 1
Implement the constant current charge-discharge test under following condition.
Discharge and recharge condition:
Charging is to carry out CC (constant current: constant current) charge, until 4.2V with 0.1C speed (complete completely charged speed in 10 hours).Discharge is to carry out the CC discharge with the speed identical with this charging rate, ends when voltage 3.0V.The later charging of next circulation, discharge are all carried out with the speed identical with this charging rate, with the 1st circulation in the same manner, end when charging voltage 4.2V, discharge voltage 3.0V.Discharge and recharge test and carry out altogether 10 circulations, with the 10th time the circulation discharge capacity be made as discharge capacity 1.
The overdischarge condition:
The battery of 10 circulations has been carried out in use, and charging is to carry out the CC charging with 0.1C speed, until 4.2V.Discharge is to carry out the CC discharge with the speed identical with this charging rate, until after voltage 0.01V, carry out CV (the constant voltage: constant voltage) discharge of 100h under voltage 0.01V.Later charging, the discharge of next circulation carried out with the speed identical with this charging rate, carries out CC to cut-off and discharge and recharge when charging voltage 4.2V, discharge voltage 3.0V.3 circulations are carried out in the test that discharges and recharges after overdischarge altogether repeatedly.
To battery pack F 1, carry out constant current charge-discharge test, over-discharge test under condition above-mentioned discharging and recharging, measure the sustainment rate of the discharge capacity of each circulation.
Discharge capacity sustainment rate (%)=discharge capacity/discharge capacity 1 * 100
Consequently, after overdischarge, the discharge capacity sustainment rate reduces sharp.
Embodiment 1
(1) anodal making
Use sodium carbonate (Na 2CO 3: purity 99.8%), manganese oxide (IV) (MnO Wako Pure Chemical Industries, Ltd.'s system: 2: purity 99.9%), oxidation iron (II, III) (Fe Co., Ltd.'s high-purity chemical institute system: 3O 4: purity 99%) and nickel oxide (II) (NiO: Co., Ltd.'s high-purity chemical institute system: purity 99%) Co., Ltd.'s high-purity chemical institute system:, the mol ratio of so that Na: Mn: Fe: Ni is 1: 0.4: 0.2: 0.4 mode weighing obtained raw mix with dry ball mixing 4 hours.Be filled in alumina boat by the raw mix with gained, use electric furnace to heat in air atmosphere and kept 6 hours under 900 ℃, obtain positive active material A 2(NaMn 0.4Fe 0.2Ni 0.4O 2).In addition, use acetylene black as conductive agent (electrochemical industry Co., Ltd. system), as the PVdF (Kureha of Co., Ltd. system) of binding agent, to reach positive active material A 2: conductive agent: the mode of the composition of binding agent=85: 10: 5 (weight ratio) is weighing positive active material A respectively 2, conductive agent and binding agent, obtain anode mixture.At first with positive active material A 2Mix fully in agate mortar with conductive agent, add in right amount METHYLPYRROLIDONE (NMP: Tokyo HuaCheng Industry Co., Ltd's system), then add PVdF, then mix, obtain slurries in this mixture.Use applicator to be coated on aluminium foil as the thick 40 μ m of positive electrode collector with the thickness of 100 μ m in the slurries of gained, put it in drying machine, by when removing NMP, carry out drying fully and obtain positive plate.Use roll squeezer to carry out fixedization of coating layer this positive plate.In addition, with ultrasonic welding machine welding Al paper tinsel, it as contact conductor, is obtained anodal B 2
(2) making of negative pole
Make resorcinol and benzaldehyde polymerization reaction.
Flow down at nitrogen in the four-hole boiling flask and add resorcinol 200g, methyl alcohol 1.5L, benzaldehyde 194g, ice bath is cooling, drips 36% hydrochloric acid 36.8g when stirring.Be warmed up to 65 ℃ after dripping end, be incubated at the same temperature 5 hours thereafter.Add entry 1L in the polymerization reaction mixture of gained, leach precipitation, water cleans to filtrate and becomes neutrality, and drying obtains tetraphenyl cup [4] resorcinol aromatic hydrocarbons (the following PCRA that sometimes is called.)294g。PCRA is added in rotary furnace, atmosphere is made as air atmosphere, heating is 1 hour under 300 ℃, and then the atmosphere with rotary furnace is replaced into argon gas, and heating is 4 hours under 1000 ℃.Then, by pulverize the material with carbon element C that obtains as negative electrode active material with ball mill (agate ball processed, 28rpm, 5 minutes) 2To reach material with carbon element C 2: binding agent PVdF=95: this material with carbon element of mode weighing C of the composition of 5 (weight ratios) 2PVdF with as binding agent obtains cathode agent, and binding agent is dissolved in as after in the NMP of solvent, adds material with carbon element C 2, slurried materials'use applicator is coated on Copper Foil as the thick 10 μ m of negative electrode collector with the thickness of 100 μ m, put it in drying machine, dry fully by when removing NMP, and obtain negative plate.Use roll squeezer to carry out fixedization of coating layer this negative plate.In addition, with ultrasonic welding machine welding Ni paper tinsel, it as contact conductor, is obtained negative pole D 2
(3) making of monocell
Aluminium foil is placed anodal B down 2, stacked polypropylene porous film as barrier film (thick 20 μ m), the negative pole D that Copper Foil is placed up 2, obtain the electrode group.The electrode group is inserted in the battery case (lamination Al bag) that the film by the thickness of 10 μ m consists of.
Will be as the NaClO of the 1M of nonaqueous electrolytic solution 4/ propylene carbonate is injected in battery case after described electrode insertion group, by carrying out the vacuum lamination sealing, produces sodium ion secondary battery E 6And, carry out in the glove box that is assembled in argon gas atmosphere of test cell.So that the charging capacity of the negative pole of per unit area with respect to the charging capacity of the positive pole of per unit area be more than 1 below 2, be preferably more than 1.0 below 1.2, more preferably more than 1.0, the mode addition weight below 1.1 makes up.
Here said " charging capacity of the positive pole of per unit area " refers to, with the current value of 0.1C with constant current charge to 4.0V (with respect to sodium to electrode), according to this charging, calculate the charging capacity of per unit area.In addition, said " charging capacity of the negative pole of per unit area " refer to, with the current value of 0.05C with constant current charge to 0.5mV (with respect to sodium to electrode), according to this charging, calculate the charging capacity of per unit area.
(4) making of battery pack
Make and sodium ion secondary battery E 6Identical battery E 7, E 8, E 9, E 10, all in parallel, obtain battery pack F 2
Implement the constant current charge-discharge test under following condition.
Discharge and recharge condition:
Charging is to carry out CC (constant current: constant current) charge, until 4.0V with 0.1C speed (speed of fully charging in 10 hours).Discharge is to carry out the CC discharge with the speed identical with this charging rate, ends when voltage 1.5V.Later charging, the discharge of next circulation carried out with the speed identical with this charging rate, and be identical with the 1st circulation, ends when charging voltage 4.0V, discharge voltage 1.5V.Discharge and recharge test and carry out altogether 10 circulations, with the 10th time the circulation discharge capacity be made as discharge capacity 1.
The overdischarge condition:
The battery of 10 circulations has been carried out in use, and charging is carried out the CC charging with 0.1C speed, until 4.0V.Discharge is carried out CC discharge with the speed identical with this charging rate, until after voltage is 0.01V, carry out CV (the constant voltage: constant voltage) discharge of 100h when voltage 0.01V.Later charging, the discharge of next circulation carried out with the speed identical with this charging rate, carries out CC to cut-off and discharge and recharge when charging voltage 4.0V, discharge voltage 1.5V.3 circulations are carried out in the test that discharges and recharges after overdischarge altogether repeatedly.
For battery pack F 2, carry out constant current charge-discharge test, over-discharge test under condition above-mentioned discharging and recharging, measure the sustainment rate of the discharge capacity of each circulation.
Discharge capacity sustainment rate (%)=discharge capacity/discharge capacity 1 * 100
Consequently, even after overdischarge, compare the discharge capacity sustainment rate with comparative example 1 and also do not reduce.
Embodiment 2
(1) anodal making
In polypropylene beaker processed, add potassium hydroxide 120g in distilled water 700mL, utilize and stir its dissolving, prepare potassium hydroxide aqueous solution (the precipitation reagent aqueous solution).In other polypropylene beaker processed, in distilled water 700mL, add sulfuric acid iron (II) heptahydrate 100g, nickelous sulfate (II) hexahydrate 71.0g and manganese sulfate (II) pentahydrate 65.1g, utilize and stir its dissolving, obtain containing the mixed aqueous solution of iron, nickel and manganese.By when stirring the described precipitation reagent aqueous solution, add wherein described mixed aqueous solution, and obtain having generated sedimentary slurries.Then, filter this slurries, clean with distilled water, reclaim solid constituent.This solid constituent is dry and be precipitated thing (mol ratio of Mn: Fe: Ni is 0.3: 0.4: 0.3) under 100 ℃.Use sediment and NaOH, so that Na: Mn: Fe: the mol ratio of Ni is 1: 0.3: 0.4: after 0.3 mode weighing, use agate mortar that the mixing of their dry types is obtained mixture.Then, add the oxidation aluminum to burn till in container in this mixture, kept 12 hours with 850 ℃ in blanket of nitrogen by using electric furnace, and this mixture is burnt till, cool to room temperature obtains positive active material A 3(NaMn 0.3Fe 0.4Ni 0.3O 2).
To reach positive active material A 3: electric conducting material acetylene black: the mode of the composition of binding agent=90: 5: 5 (weight ratio) is weighing positive active material A respectively 3, as the acetylene black of electric conducting material (electrochemical industry Co., Ltd. system) and binding agent (VT470, Daikin Industrial Co., Ltd system).Thereafter, at first with positive active material A 3Mix fully in agate mortar with electric conducting material, add METHYLPYRROLIDONE (NMP: Tokyo HuaCheng Industry Co., Ltd's system), then add binding agent, then mix, obtain the anode mixture paste in agate mortar in this mixture.Use applicator to be coated on aluminium foil as the thick 20 μ m of collector body with the thickness of 100 μ m the anode mixture paste.The collector body that has been coated with after under 60 ℃ dry 2 hours, is cut into 4cm wide, by with the electrode of gained with roll squeezer (SA-602, Tester Industry Co., Ltd system) with the 0.5MPa calendering, and obtain electrode slice.Be the circle of diameter 1.45cm with this electrode slice with electrode clicker press machine stamping-out, 150 ℃ of lower vacuumizes 8 hours, obtain surface density slightly different anodal B each other 3And B 4So-called surface density refers to the active material weight of per unit area.
(2) making of negative pole
Use is as the material with carbon element C of negative electrode active material 3(Japanese Carbon company system, trade name: Nikabeads ICB-0510) with as the Sodium Polyacrylate (Wako system, the degree of polymerization 22,000～70,000) of binding agent, as the water of solvent, produce the cathode agent paste.The binder aqueous solution that making is dissolved in the water this binding agent is to reach negative electrode active material C 3: binding agent: the mode weighing of the composition of water=97: 3: 150 (weight ratio), stir, mix by using Dispermat (VMA-GETZMANN company system), and obtain the cathode agent paste.The rotating condition of rotating vane is made as 2,000rpm, 5 minutes.Use scraper for coating on Copper Foil the cathode agent paste of gained, after under 60 ℃ dry 2 hours, use roll squeezer (SA-602, Tester Industry Co., Ltd system) to obtain electrode slice with the 0.5MPa calendering by being cut into the wide electrode of 4cm.Be the circle of diameter 1.50cm with this electrode slice with electrode clicker press machine stamping-out, 100 ℃ of lower vacuumizes 8 hours, obtain surface density slightly different negative pole D each other 3And D 4
(3) making of monocell
At the recess of the lower side member of button cell (precious Izumi Ltd. system), aluminium foil is placed anodal B down 3, stacked polypropylene porous film as barrier film (thick 20 μ m), the negative pole D that Copper Foil is placed up 3, inject the NaClO as the 1M of nonaqueous electrolytic solution 4/ propylene carbonate is riveted after making up upper side member, and is produced sodium ion secondary battery E 11And, carry out in the glove box that is assembled in argon gas atmosphere of test cell.Similarly use anodal B 4With negative pole D 4Obtain sodium ion secondary battery E 12
At sodium ion secondary battery E 11In, the charging capacity of the negative pole of per unit area is 1.07 with respect to the charging capacity of the positive pole of per unit area.At sodium ion secondary battery E 12In, the charging capacity of the negative pole of per unit area is 1.05 with respect to the charging capacity of the positive pole of per unit area.
Here said " charging capacity of the positive pole of per unit area " refers to, with the current value of 0.1C (in 10 hours fully charging speed) with constant current charge to 4.0V (with respect to sodium to electrode), according to this charging, calculate the charging capacity of per unit area.In addition, said " charging capacity of the negative pole of per unit area " refers to, with the current value of 0.05C (in 20 hours fully charging speed) with constant current charge to 0.5mV (with respect to sodium to electrode), according to this charging, calculate the charging capacity of per unit area.
(4) making of battery pack
With sodium ion secondary battery E 11With battery E 12Parallel connection obtains battery pack F 3
To battery pack F 3, implemented the constant current charge-discharge test under following condition.
Discharge and recharge condition:
Charging is to carry out CC (constant current: constant current) charge, until 4.0V with 0.1C speed.Discharge is to carry out the CC discharge with the speed identical with this charging rate, ends when voltage is 1.5V.Later charging, the discharge of next circulation carried out with the speed identical with this charging rate, and be identical with the 1st circulation, ends when charging voltage 4.0V, discharge voltage 1.5V.Discharge and recharge test and carry out altogether 10 circulations, with the 10th time the circulation discharge capacity be made as discharge capacity 1.
The overdischarge condition:
The battery of 10 circulations has been carried out in use, and charging is to carry out the CC charging with 0.1C speed, until 4.0V.Discharge is to carry out CC discharge with the speed identical with this charging rate, until after voltage is 0.01V, carry out CV (the constant voltage: constant voltage) discharge of 100h under voltage 0.01V.Later charging, the discharge of next circulation carried out with the speed identical with this charging rate, carries out CC to cut-off and discharge and recharge when charging voltage 4.0V, discharge voltage 1.5V.3 circulations are carried out in the test that discharges and recharges after overdischarge altogether repeatedly.
To battery pack F 3, carry out constant current charge-discharge test, over-discharge test under condition above-mentioned discharging and recharging, determine the sustainment rate of the discharge capacity of each circulation.
Discharge capacity sustainment rate (%)=discharge capacity/discharge capacity 1 * 100
Consequently, the discharge capacity sustainment rate of the circulation of each after overdischarge is 100%.
Utilizability on industry
Battery pack of the present invention has the deteriorated effect that is difficult to cause the battery performance that is caused by overdischarge, and is very useful with power supply etc. as power supply or the electric power equalization of electric motor car.

Claims (4)

1. a battery pack, be that a plurality of monocells are interconnected the battery pack that forms, it is characterized in that,
Described monocell is to have to comprise positive pole, negative pole and the electrolytical sodium ion secondary battery that can adulterate, remove the positive active material of sodium contaminated ion.
2. battery pack according to claim 1, wherein,
Described positive active material is the sodium transistion metal compound that can adulterate, go the sodium contaminated ion.
3. battery pack according to claim 2, wherein,
Described sodium transistion metal compound is with NaM 1O 2The oxide of expression, wherein M 1The transition metal of expression more than a kind.
4. the described battery pack of any one according to claim 1～3, wherein,
Comprise at least one parallel connection.
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