CN1495958A - Nonaqueous electrolyte battery - Google Patents

Nonaqueous electrolyte battery Download PDF

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Publication number
CN1495958A
CN1495958A CNA031327443A CN03132744A CN1495958A CN 1495958 A CN1495958 A CN 1495958A CN A031327443 A CNA031327443 A CN A031327443A CN 03132744 A CN03132744 A CN 03132744A CN 1495958 A CN1495958 A CN 1495958A
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nonaqueous electrolytic
electrolytic battery
rechargeable nonaqueous
active material
record
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CN1327566C (en
Inventor
渡边俊二
实
菅野佳实
夫
酒井次夫
之
小关裕之
太郎
金谷孝太郎
早坂丰夫
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Seiko Instruments Inc
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SII Micro Parts Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Sealing Battery Cases Or Jackets (AREA)
  • Cell Separators (AREA)

Abstract

To solve the problem wherein a nonaqueous electrolyte secondary battery, using a niobium oxide and a lithium aluminum alloy as electrode active materials, cannot cope with the demands for voltage reduction. The nonaqueous electrolyte secondary battery uses a niobium oxide as the positive electrode active material and a material including Si as a negative electrode active material. The use of Si and SiO as the negative electrode active material, having a charge/discharge curve with a slope, as compared to conventional lithium aluminum alloys, which has a sloping charge/discharge curve to the battery, thereby providing a nonaqueous electrolyte secondary battery which can cope with various demands for equipment manufacturers for voltage reduction.

Description

Rechargeable nonaqueous electrolytic battery
Technical field
The present invention relates to adopt Coin shape (button type) rechargeable nonaqueous electrolytic battery of the nonaqueous electrolyte of lithium ion conductive can occlusion deviating from the active material of the material of lithium as negative pole and positive pole.
Background technology
In the past, Coin shape (button type) rechargeable nonaqueous electrolytic battery owing to have the feature of high-energy-density, light weight, therefore as the purposes of the stand-by power supply of machine in continuous increase.The rechargeable nonaqueous electrolytic battery that memory and timer are standby is to be charged to more than the 3V.But along with the lower voltage of machine, the standby secondary cell of memory and timer also must be a low-voltage.Now, as the battery that can charge under low-voltage, mainly contain with niobium oxide as positive active material, lithium-aluminium alloy is as the battery (for example, referring to Patent Document 1) of negative electrode active material.
Patent documentation 1
Te Kaiping 2000-133313 communique (2-4 page or leaf)
Along with the lower voltage of machine, the standby secondary cell of memory and timer also must be a low-voltage.But, the requirement of lower voltage, disunity owing to machine maker's design philosophy difference.That is to say, charging voltage, the final discharging voltage of the machine of rechargeable nonaqueous electrolytic battery is housed, because employed electronic unit, the power supply that adopted, and vary.Particularly, to the system development of 3V series～2.5V series, now because the various parts that the machine maker selects for use the performance with cost and machine to be complementary, in fact therefore charging voltage, the final discharging voltage (battery-operated voltage range) of the machine of rechargeable nonaqueous electrolytic battery are housed, because of each machine maker, further different because of every machine.
But,, therefore can not require with the lower voltage of each company to adapt owing to being positive active material with the niobium oxide originally, being the rechargeable nonaqueous electrolytic battery of negative electrode active material with the lithium-aluminium alloy that its discharge curve demonstrated comparatively level and smooth characteristic.Be positive active material, as the charging and discharging curve of the rechargeable nonaqueous electrolytic battery (diameter 6.8mm, high 1.4mm) of negative electrode active material as shown in Figure 2 originally with lithium-aluminium alloy with the oxide of niobium.As shown in Figure 2, demonstrate the rechargeable nonaqueous electrolytic battery of level and smooth charging and discharging curve, battery-operated voltage range is very narrow.That is to say, when charging,, then on the negative pole of lithium-aluminium alloy, separating out unusually of lithium will be taken place,, then can not charge fully if certain voltage of voltage ratio is low if adopt high voltage.When discharge, owing to use lithium-aluminium alloy in the negative pole, if therefore carry out deep discharge, then lithium alloy deterioration, cycle life significantly worsen.If final discharging voltage rises a little, then almost can not get discharge capacity.Therefore, in the characteristic of Fig. 2, more than using 1.0V, sufficient discharge capacity can be guaranteed during less than the voltage of 1.5V, but during the voltage more than using 1.5V, then discharge capacity can not be made full use of.
In addition, originally the oxide with niobium be positive active material, with the rechargeable nonaqueous electrolytic battery of lithium-aluminium alloy as negative electrode active material owing to there be use not consider heat-resisting material, so during reflow soldering, have the shortcoming of cell performance loss.
Summary of the invention
The present invention makes charging and discharging curve have gradient in order to solve above-mentioned problem.Therefore, the present invention uses niobium oxide, negative electrode active material use to contain the Si material in positive active material.Compare with original lithium-aluminium alloy, have Si, SiO, the WO of gradient charging and discharging curve by use 2, WO 3As negative electrode active material, the charging and discharging curve of battery also becomes and has gradient.Thus, can provide various low-voltages with the machine maker to require the rechargeable nonaqueous electrolytic battery that adapts.
That is to say, rechargeable nonaqueous electrolytic battery of the present invention, it is characterized in that, have positive pole, negative pole, nonaqueous solvents, contain electrolyte, dividing plate and the packing ring of supporting salt, simultaneously anodal contained positive active material comprises niobium oxide, and contained negative electrode active material comprises the material that contains Si or W in the negative pole.Its feature is that also niobium oxide is Nb 2O 5Its feature is that also niobium oxide is Nb heat treated under the temperature below 900 ℃ more than 600 ℃ 2O 5
Perhaps, it is characterized in that Nb 2O 5Be to contain oxidation price ratio Nb 2O 5The niobium oxide of low niobium heats under the temperature below 900 ℃ more than 600 ℃ and generates.Its feature also is, contains oxidation price ratio Nb 3O 5The niobium oxide of low niobium is NbO or NbO 2
In addition, it is characterized in that niobium oxide is niobic acid to be heated and the Nb that generates under the temperature below 900 ℃ more than 600 ℃ 2O 5
And, it is characterized in that, the anode mixture of niobium oxide, perhaps, the positive pole of niobium oxide is more than 200 ℃, heat-treat below 300 ℃.Its feature is that also contained adhesive is water miscible in the anode mixture of niobium oxide.
In addition, it is characterized in that negative electrode active material is more than one the active material that is selected among SiO and the Si.Perhaps, it is characterized in that negative electrode active material is SiO.And negative electrode active material is SiO, the Si oxide that contains lithium that can electrochemistry occlusion lithium in negative electrode active material, and its composition formula is by Li xSiO represents that the content x of lithium is 4.0≤x≤4.5.
In addition, adapt, also have thermal endurance as electrolyte, dividing plate, the packing ring of the inscape of battery with reflow soldering, even and with the assembling of electrode in, find also not loss of battery performance.Coin shape (button type) rechargeable nonaqueous electrolytic battery of anti-reflux temperature can be provided thus.
That is to say that rechargeable nonaqueous electrolytic battery of the present invention is to be equipped with to contain Nb 2O 5As the positive pole of active material, contain and be selected from WO 2, WO 3, among the SiO more than one active material negative pole, under normal pressure boiling point be more than 200 ℃ nonaqueous solvents, to contain electrolyte, the heat distortion temperature of supporting salt be that dividing plate more than 230 ℃ and heat distortion temperature are the packing ring more than 230 ℃.Have again, support that salt contains fluorine element.Specifically, in supporting salt, use is selected from hexafluoro and closes lithium phosphate (LiPF 6), LiBF4 (LiBF 4) in separately or compound.
In addition, in nonaqueous solvents, use the independent or compound that is selected from ethylene carbonate (EC), the gamma-butyrolacton (γ BL).
Secondly, it is resin more than 230 ℃ that dividing plate contains glass fibre or heat distortion temperature, and packing ring to contain heat distortion temperature be resin more than 230 ℃.Specifically, as the heat distortion temperature that is used for dividing plate or packing ring is that resin more than 230 ℃ can use p-poly-phenyl thioether, liquid crystal polymer (LCP), polyether-ether-ketone resin (PEEK), polyethers nitrile resin (PEN), polyamide-imide resin or tetrafluoroethene-perfluoroalkyl vinyl ether copolymer resins.
The simple declaration of drawing
Fig. 1
The sectional drawing of representing Coin shape lithium secondary battery of the present invention.
Fig. 2
The chart of discharge curve in the expression rechargeable nonaqueous electrolytic battery in the past.
Fig. 3
The chart of the discharge curve when the heating generation temperature of expression active material changes.
Fig. 4
The chart of the discharge curve the when heat treatment temperature of expression mixture changes.
Fig. 5
The chart of the charging and discharging curve of the battery of expression embodiment 1 and comparative example 1.
Fig. 6
The charging and discharging curve of the battery of embodiment 4.
The explanation of symbol
101 positive plates
102 electrode current collector
103 anodal housings
104 negative plates
105 negative pole housings
106 lithium paper tinsels
107 electrolyte
108 packing rings
109 dividing plates
110 fluid sealants
The working of an invention scheme
Rechargeable nonaqueous electrolytic battery of the present invention has gradient in order to make charging and discharging curve, uses SiO and Si in the negative electrode active material.Particularly, owing to use SiO, it is big that the gradient of charging and discharging curve can become.In addition, when using SiO to make battery, need with the occlusion in advance of transportable lithium ion in SiO, form with Li xThe Si oxide that contains lithium that SiO represents.In such cases, because the content of lithium increases, so the current potential of negative side descends, and the charging and discharging curve inclination that becomes.Simultaneously, even also chargeable under the high voltage.If the lithium that occlusion is too much, the lithium metal is separated out from electrode unusually when then charging, so x is that the scope of 4.0≤x≤4.5 is preferred.In addition, when adopting Si as negative electrode active material, it is effective using the material that mixes carbon dust and fix with resin binder in the Si powder.
Positive active material is a niobium oxide, Nb 2O 5Capacity is big, favourable.Nb to heating generation under the different temperatures 2O 5,, thereby make the electrode that solid measure is used with graphite and adhesive mixing manufacture mixture mutually.Use Li as opposed negative pole with it, and the manufacturing test battery.In the test battery of having measured capacity, the battery of 800 ℃ and 1000 ℃, it the results are shown among Fig. 3.Heat the Nb that generates down at 1000 ℃ 2O 5Big with the specific capacity mutually that heats generation down at 800 ℃, the inclination of discharge curve is also little.
Discharge capacity under the different heating generation temperature has been shown in the table 1.
Table 1
Heating generates temperature ?550℃ ?600℃ ?700℃ ?800℃ ?850℃ ?900℃ ?1000℃ ?1100℃
Discharge capacity mAh/g final voltage 1V ?155 ?178 ?183 ?184 ?190 ?210 ?229 ?230
Cycle characteristics ?△ ?○ ?○ ?○ ?○ ?◎ ?◎ ?◎
By table 1 as seen, raise because heating generates temperature, it is big that capacity becomes.Not only capacity is big but also cycle characteristics might as well when heating generates more than 600 ℃ in discovery.The actual use of zero of record expression gone up no problem level in the table 1, and ◎ represents good especially level.For the gradient of discharge curve, change in the time of about 900 ℃.If surpass 900 ℃, gradient minimizing 1000 ℃ the discharge curve then as among Fig. 3.By just becoming clear below the above summary.
If use the Nb that heating generates under the high temperature more than 900 ℃ 2O 5, then not only capacity becomes big but also cycle characteristics is good.But, have gradient in order to make charging and discharging curve, it is effective heating generation down at 600 ℃～900 ℃.Particularly, when heating generated in 700 ℃～850 ℃ scope, the gradient of capacity, charging and discharging curve and cycle characteristics were all good.
When the preparation niobium oxide, contain oxidation price ratio Nb 2O 5The niobium oxide of low niobium or niobium hydroxide generate through heating, can obtain stable Nb 2O 5But wherein, by NbO, NbO 2What generate with niobic acid is stable.
In addition, find under the situation of the oxide that uses niobium, under reflux temperature, to be stable.Particularly, use Nb 2O 5The time be stable.Though principle understands as yet, under the situation of niobium oxide, have and make the negative pole stabilisation at high temperature that contains lithium as positive pole, significantly suppress the effect of cell expansion, internal resistance rising.
Electrolyte as electrolyte can use gamma-butyrolacton, propene carbonate, ethylene carbonate, butylene, dimethyl carbonate, diethyl carbonate, ethylene methyl esters, methyl formate, 1, the independent or mixed solvent in the organic solvents such as 2-dimethoxy-ethane, oxolane, dioxolanes, dimethyl formamide.
Find that when carrying out reflow soldering as electrolyte, use boiling point under normal pressure is that the nonaqueous solvents more than 200 ℃ is stable under reflux temperature.Reflux temperature is elevated to about 250 ℃ sometimes, and the pressure of inside battery rises under this temperature, even the result uses boiling point under the normal pressure when being 204 ℃ gamma-butyrolacton (γ BL), battery can not break yet.In the assembling of both positive and negative polarity, preferred independent a kind of or its compound that is selected from propene carbonate (PC), ethylene carbonate (EC), the gamma-butyrolacton (γ BL) that uses.
In addition, also can use polymer except that above-mentioned organic solvent.As polymer, can use present normally used material.For example, the preferred use: poly(ethylene oxide) (PEO), PPOX, the crosslinked body of polyethyleneglycol diacrylate, Kynoar, the crosslinked body of polyphosphazene, the crosslinked body of polypropyleneglycol diacrylate, the acrylate cross linked body of methoxypolyethylene glycol, the acrylate cross linked body of polypropylene glycol methyl ether etc.
Can exemplify out as the major impurity that in electrolyte (nonaqueous solvents), exists: moisture, organic peroxide (for example, glycols, alcohols, carbonic acid class) etc.Consider that these impurity form dielectric film on the surface of active material, electrode interface resistance is increased.The worry that therefore, the influence of cycle life of causing and capacity reduction is arranged.The worry that self discharge increases when in addition, also having high temperature (more than 60 ℃) to store.Thus, in containing the electrolyte of nonaqueous solvents, preferably reduce impurity as far as possible.Specifically, moisture is below the 50ppm, and organic peroxide is to be preferred below the 1000ppm.
As supporting salt, can use lithium perchlorate (LiClO 4), hexafluoro closes lithium phosphate (LiPF 6), tetrafluoro closes lithium borate (LiBF 4), hexafluoro closes arsenic acid lithium (LiAsF 6), the inclined to one side sulfonic acid lithium of trifluoro (LiCF 3SO 3), bis trifluoromethyl sulphonyl imino group lithium [LiN (CF 3SO 2) 2], more than one the salt in the lithium salts (electrolyte) of thiocyanates, aluminum fluoride salt etc. etc.When carrying out reflow soldering, with LiClO 4Compare etc. chloride material, the support salt that contains fluorine element is that hexafluoro closes lithium phosphate (LiPF 6), tetrafluoro closes lithium borate (LiBF 4), the inclined to one side sulfonic acid lithium of trifluoro (LiCF 3SO 3) no matter be that heat or electrical characteristics are all stable.Its meltage with respect to nonaqueous solvents is preferably 0.5～3.0 mol.
Use the film that has high ion permeability, has predetermined mechanical strength and insulating properties as dividing plate.Scope commonly used in the battery is adopted in the aperture of dividing plate.For example, adopt 0.01～10 μ m.The thickness of dividing plate adopts normally used scope in the battery, as 5～300 μ m.
Packing ring uses polypropylene etc. usually.When carrying out reflow soldering, polyphenylene sulfide, PETG, polyamide, liquid crystal polymer (LCP), tetrafluoroethene-perfluoroalkyl vinyl ether copolymer resins (PFA), polyether-ether-ketone resin (PEEK), polyethers nitrile resin (PEN), polyether ketone resin (PEK), polyamidoimide, poly-allylat thing (the resin of Port リ ア リ レ-ト), the polybutylene terephthalate (PBT) resin, poly-cyclohexanedimethyleterephthalate terephthalate resin, polyethersulfone resin, poly-amino dimaleimide (Port リ ア ミ ノ PVC ス マ レ イ ミ De) resin, polyetherimide resin, fluororesin, under reflux temperature, do not break etc., and the back of refluxing does not take place because gasket deforms causes problems such as leak of liquid when preserving yet.
Particularly, heat distortion temperature is the resin more than 230 ℃, polyphenylene sulfide, liquid crystal polymer (LCP), polyether-ether-ketone resin (PEEK), polyethers nitrile resin (PEN), polyamide-imide resin or tetrafluoroethene-perfluoroalkyl vinyl ether copolymer resins, good aspect anti-leak of liquid.In addition, the glass fibre below can in this material, adding about 40 weight %, mica whisker, ceramic, ceramic whisker etc.Particularly preferably use the whisker of potassium titanate.
Manufacture method as packing ring has hot compression method and extrusion moulding etc.
The hot compression method be with than the thick heavy-gauge sheeting of formed products washer-shaped as the raw material formed products, below fusing point, carry out hot compression and be shaped, obtain the method for final molding product.
Usually, if, then have the character of restoring to the shape of original raw material formed products to by the formed products heating of the thermoplastic resin of shaping to being shaped under the temperature below the fusing point of raw material formed products through hot compression.Thus, if original words, between tank body and interior tank body (metal) and the packing ring (resin) gap appears outside, perhaps between tank body and packing ring, can not obtain enough Sealing Stress, in such rechargeable nonaqueous electrolytic battery, by using this packing ring, because heat treatment (reflow soldering etc.) causes the expansion of packing ring, very close to each other between outer tank body and interior tank body (metal) and the packing ring (resin), perhaps obtain sufficient Sealing Stress between tank body and the packing ring.In addition, have after after a while and restore, even also effective the battery beyond the reflow soldering to the character of raw material formed products original form.
Particularly, in the packing ring that uses tetrafluoroethene-perfluoroalkyl vinyl ether copolymer resins (PFA), compare with the packing ring that makes by extrusion molding, flaky material is good through the sealing property of the hot compression formed products that heating and pressurizing is made.If this is because PFA has caoutchouc elasticity, then extrusion molding article shrinks under reflux temperature, and is relative therewith, and the hot compression formed products restores the sheet thickness before extremely being shaped under reflux temperature, therefore the internal pressure of closure part rises, and can reach that more to advance sealing of one deck airtight.
On the other hand, the extrusion molding method is the most frequently used as the manufacturing process of packing ring.But, sacrificing under the situation of forming accuracy by reducing cost etc., must assist and use fluid sealant to carry out airtight.
Under the situation of coin, button cell, use a kind of or mixture in pitch, fourth rubber, fluorine-containing oil, chlorosulfonated polyethylene, epoxy resin etc. between packing ring and the positive and negative electrode tank body as fluid sealant.Fluid sealant be carry out under the transparent situation painted, clear and definite whether the coating.Cladding process as sealant has the agent of the washer sealing of injection, applies impregnating in the sealant solution of packing ring on the positive and negative electrode tank body.
When battery be shaped as coin and button shaped the time, the shape of electrode can be compressed into the mixture of positive active material and negative electrode active material tabular the use.In addition, when being slim coin and button, also the electrode that is configured as sheet can being carried out punching and use.The thickness of this plate and diameter are by the size decision of battery.
The pressure method of plate can adopt normally used method, still, and the method for special preferred mold pressurization.The pressure of pressurization is not particularly limited, and is preferably 0.2～5 ton/cm 2Pressed temperature is preferably room temperature～200 ℃.
In electrode composition, can add conductive agent and adhesive and filler etc.The kind of conductive agent is not particularly limited, and can be metal dust, but preferred especially carbon class material.Material with carbon element uses native graphite (flaky graphite, flaky graphite, amorphous graphite etc.), Delanium, carbon black, channel black, thermal black, furnace black, acetylene black, carbon fiber etc.In addition, metal uses metal powder, the metallic fiber of copper, nickel, silver etc.Also can use electroconductive polymer.
The addition of carbon, mixing ratio though be not particularly limited, are under the situation of negative pole along with the conductivity of active material, electrode shape etc. and different, are preferably 1～50 weight %, are preferably 2～40 weight % especially.The particle diameter of carbon in average grain diameter in the scope of 0.5～50 μ m, preferably in the scope of 0.5～15 μ m, more preferably in the scope of 0.5～6 μ m, the contact between this moment and the active material is good, improved the formation of conductive network, the active material irrelevant with electrochemical reaction reduces.
Adhesive is preferably material insoluble in electrolyte.Can use polyacrylic acid and polyacrylic acid corrective; polyvinyl alcohol; carboxymethyl cellulose; starch; hydroxypropyl cellulose; regenerated cellulose; diacetyl cellulose; polyvinyl chloride; PVP; tetrafluoroethene; Kynoar; polyethylene; polypropylene; ethene-propylene-diene polymer (EPDM); sulfonated epdm; styrene butadiene ribber; polybutadiene; fluorubber; poly(ethylene oxide); polyimides; epoxy resin; polysaccharides such as phenolic resins; thermoplastic resin; heat reactive resin; has a kind of or its mixture in the polymer etc. of caoutchouc elasticity.The addition of adhesive is preferably 1～50 weight %.
By using water miscible adhesive, can alleviate burden to environment.In the preparation of anode mixture, when using water-soluble polypropylene acid and polyacrylic acid corrective, polyethylene glycol, carboxymethyl cellulose, starch etc., owing to Nb 2O 5Therefore suction must heat-treat the plate of anode mixture or anode mixture shaping.
For heating the Nb that generates down at 800 ℃ 2O 5, with graphite and adhesive (polyacrylic acid; Water-soluble) mix preparation mixture, thereby preparation solid measure electrode (plate) mutually.The electrode that makes for drying, in atmosphere under predetermined temperature, heat treatment 8 hours.Use Li as opposed negative pole with it, with the preparation test battery.
The result of capacity etc. under the different heat treatment temperatures has been shown in the table 2.
Table 2
Heat treatment temperature 150℃ ?200℃ ?250℃ ?300℃ ?310℃
Discharge capacity mAh/g final voltage 1V 119 ?178 ?184 ?185 ?185
Plate intensity ◎ ?◎ ?○ ?○ ?△
Heat-treating no problem capacity when having obtained above actual use of 170mAh/g more than 200 ℃.The intensity of plate shown in the table 2, wherein ◎ or zero is a level no problem in the actual use, △ is the level that is easy to generate breakage, causes producing obstacle.In order to make capacity stable, heat treatment temperature raises and helps removing Nb 2O 5In moisture, begin to decompose the intensity variation of plate but organic substance is an adhesive.In addition, the charging and discharging curve of heat treatment temperature under 150 ℃ and 250 ℃ as shown in Figure 4.By above summary, it is clear below will to become.
Discovery is being heat-treated below 200 ℃, and capacity is low, but heat-treats at 200 ℃～300 ℃, and capacity rises.Yet, heat-treating more than 300 ℃, because the intensity of plate reduces, can't actually use.
Filler is not so long as cause that for the battery that constitutes the fibrous material of chemical change gets final product, and can use any material.Under the situation of the present invention, can use the fiber of carbon, glass etc.The addition of filler is not particularly limited, and is preferably 0～30 weight %.
As the tank body that has the electrode active material current-collector concurrently, preferably use the little metallic plate of resistance.For example, in positive pole,, except that stainless steel, nickel, aluminium, titanium, tungsten, gold, platinum, carbon electrode etc., can use the material of on aluminium and stainless surface, handling through carbon, nickel, titanium or silver as material.The stainless steel two-phase is stainless to be effective for anticorrosion.Under the situation of coin, button cell, the nickel plating of outside batteries side.Have as processing method: wet method plating, dry method plating, CVD, PVD, carry out clad, coating etc. by extrusion.
In negative can,, except that stainless steel, nickel, copper, titanium, aluminium, tungsten, gold, platinum, carbon electrode etc., can use the material of on copper and stainless surface, handling, Al-Cd alloy etc. through carbon, nickel, titanium or silver as material.Have as processing method: wet method plating, dry method plating, CVD, PVD, carry out clad, coating etc. by extrusion.
The tank body of electrode active material and current-collector can be fixed by conductive adhesive.Can use material that in the resin that is dissolved in solvent, adds the material of carbon, metal dust and fiber and be dissolved with electroconductive polymer etc. as conductive adhesive.
Under the situation of plate electrode, between current-collector and battery lead plate, apply, with fixed electrode.At this moment, in most cases in conductive adhesive, contain heat reactive resin.
Purposes to rechargeable nonaqueous electrolytic battery of the present invention is not particularly limited, and is for example, at the stand-by power supply of portable phone, beep-pager etc., suitable in the machine of particularly battery-operated voltage in 2.5V～1.0V left and right sides scope.
Expect that battery of the present invention assembles removing under wet atmosphere or the inert atmosphere.In addition, assembled components is also preferably being carried out drying in advance.As to plate, sheet and other parts drying and dehydration method, preferably be used alone or in combination hot blast, vacuum, infrared ray, far infrared, electron ray and low wet wind.Temperature is preferred in 80～350 ℃ scope, is preferably especially in 100～300 ℃ the scope.In entire cell, water content is preferably below the 2000ppm, will be set in respectively in anode mixture, cathode agent and electrolyte below the 50ppm, sees it is preferred from the angle that charge improves.
Below, will illustrate in greater detail the present invention by embodiment.
Embodiment
Embodiment 1
Present embodiment uses at 800 ℃ and heats the Nb that niobic acid generates down 2O 5As positive active material, with SiO as negative electrode active material.Positive pole, negative pole and electrolyte are according to following method preparation.In addition, battery is of a size of external diameter 6.8mm, thick 1.4mm.The battery sectional drawing as shown in Figure 1.
Anodal according to following method preparation.With commercially available niobic acid (Nb 2O 5NH 2O) in atmosphere, 800 ℃ of down heating 8 hours, obtain Nb 2O 5At this Nb through pulverizing 2O 5In, with weight ratio Nb 2O 5: graphite: the mixed of polyacrylic acid=78: 20: 2 forms anode mixture as the graphite of conductive agent with as the polyacrylic acid of adhesive, secondly, with this anode mixture of 30mg at 2 tons/cm 2Following press molding is the plate of diameter 6.35mm.Positive plate 101 usefulness that so obtain are contained the electrode current collector 102 of the conductive adhesive resin of carbon containing, be adhered to integrated on the anodal housing 103 (anodal blocking) after, heat treatment is 8 hours in 250 ℃ atmosphere.
Negative pole prepares according to following method.Commercially available SiO is pulverized the back as electrode active material, mix in this active material as the graphite of conductive agent with as the polyacrylic acid of adhesive, its weight ratio separately is 45: 40: 15, forms cathode agent.With the 5.4mg mixture at 2 tons/cm 2Following press molding is the plate of diameter 4.2mm.Negative plate 104 usefulness that so obtain are contained with the electrode current collector 2 of carbon as the conductive adhesive resin of electroconductive stuffing, be adhered to integrated on the negative pole housing 105 (negative pole blocking) after, heat treatment is 8 hours in 250 ℃ of following atmosphere.Then, press onboard and be stained with the lithium paper tinsel that is stamped into the thick 0.27mm of diameter 4mm, form lithium-negative plate lamination electrode.
With thickness is that nonwoven fabrics that the glass fibre of 0.2mm constitutes strikes out φ 4.5mm after drying and forms dividing plate 109.Packing ring 108 uses the material of PP system.In electrolyte 107, use at propene carbonate (PC): ethylene carbonate (EC): 1, the volume ratio of 2-dimethoxy-ethane (DME) is to be dissolved with 1 mol lithium perchlorate (LiClO in 1: 1: 2 the mixed solvent 4) solution, this solution of 15 μ L is injected battery tank body.By with positive pole unit with the negative pole unit is stacked seals, and make battery.
Embodiment 2
Present embodiment is, with commercially available niobic acid (Nb 2O 5NH 2O) in atmosphere, 1000 ℃ of down heating 8 hours, obtain Nb 2O 5Prepare battery according to the method identical in addition with embodiment 1.
Embodiment 3
Present embodiment is, except that prepare negative pole according to following method, other is according to the method preparation identical with embodiment 1.Negative pole prepares according to following method.Commercially available Si is pulverized the back as electrode active material.In this active material, the mixed that with separately weight ratio is 45: 40: 15 is as the graphite of conductive agent, as the polyacrylic acid of adhesive, thereby makes cathode agent.With the 5.0mg mixture at 2 tons/cm 2Following press molding is the plate of diameter 4.2mm.Negative plate 104 usefulness that so obtain are contained the electrode current collector 2 of carbon as the conductive adhesive resin of electroconductive stuffing, be adhered to integrated on the negative pole housing 105 (negative pole blocking) after, heat treatment is 8 hours in 250 ℃ of following atmosphere.Then, onboard, pressure is stained with and strikes out diameter is the lithium paper tinsel 106 of 0.33mm for 4mm thickness, forms lithium-negative plate lamination electrode.
Comparative example 1
To using just very Nb 2O 5, negative pole is lithium-aluminium alloy, diameter is 6.8mm, highly studies for the commercially available battery of 1.4mm.
To the battery of the foregoing description 1～3 and the battery of comparative example 1, measure charging and discharging curve.Discharge is to carry out under the constant current discharge of 1.0V at 25 μ A, final voltage.Charging is to carry out under the 2.5V at 25 μ A, final voltage.About the value of discharge capacity, voltage difference shown in the following table 3.
Table 3
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
Anodal Active material Nb 2O 5 ?Nb 2O 5 ?Nb 2O 5 ?Nb 2O 5
Heating generates temperature 800℃ ?1000℃ ?800℃ ?-
The plate heat treatment temperature 250℃ ?250℃ ?250℃ ?-
Negative pole Active material SiO ?SiO ?Si The Li-Al alloy
Capacity (mAh) 1.5V more than 1 ?1 ?0.8 ?0.4
1.3V more than 1.5 ?1.5 ?1.4 ?0.5
1.1V more than 2.4 ?2.5 ?2.65 ?2
The battery of present embodiment 1～3 is compared with the battery of comparative example 1, and is big at 1.3V, discharge capacity more than the 1.5V.When 1.3V is above, demonstrate and be about 3 times value, when 1.5V is above, show to be about 2 times value.It is 1000 ℃ battery that anodal heating generates temperature, the discharge capacity more than 1.1V, and generating temperature with heating is that 800 ℃ embodiment 1 compares and demonstrates big some discharge capacities.Because charging and discharging curve is so big, so the discharge capacity more than 1.3V and the 1.5V does not have difference.Demonstrate the discharge capacity bigger with Si as the discharge capacity of battery more than 1.1V of the embodiment 3 of negative electrode active material than embodiment 1,2.But because charging and discharging curve is so big, so the discharge capacity more than 1.3V and the 1.5V becomes more or less low value.
The charging and discharging curve of embodiment 1 and comparative example 1 as shown in Figure 5.The battery of embodiments of the invention 1 has gradient charging and discharging curve, even the final voltage of machine that is equipped with battery also can be guaranteed discharge capacity over half for such as 1.3V the time.
In addition, about the battery of comparative example 1, when discharging and recharging of 2.5V to 1V carried out 30 times repeatedly, the performance of battery disappeared.Can think this be since the lithium-aluminium alloy that uses as negative pole because degree of depth charge and discharge cycles and due to the deterioration.In contrast, even the battery repeated charge of present embodiment 1～3 more than 100 times, the performance of battery does not disappear yet.
Embodiment 4
Present embodiment is with Nb 2O 5As positive active material, with the situation of SiO as the battery that is adapted to reflux of negative electrode active material.Use is according to positive pole, negative pole and the electrolyte of following preparation.In addition, battery is of a size of external diameter 4.8mm, thick 1.4mm.
As embodiment 4, anodal according to following method preparation.Niobic acid is heated the Nb that generates down at 800 ℃ 2O 5Material after the pulverizing with as the graphite of conductive agent, as the polyacrylic acid of adhesive with weight ratio Nb 2O 5: graphite: the mixed of polyacrylic acid=78: 20: 2 forms anode mixture, then, with this anode mixture of 6.3mg at 2 tons/cm 2Following press molding is the plate of diameter 2.4mm.Then, positive plate 101 usefulness that so obtain are contained the electrode current collector 102 of the conductive adhesive resin of carbon containing, be adhered to integrated on the anodal housing 103 (anodal blocking) after, at 250 ℃ of decompression heat dryings 8 hours down.
Negative pole prepares according to following method.With the active material of the material after the commercially available SiO pulverizing as electrode.Mix as the graphite of conductive agent, as the polyacrylic acid of adhesive in this active material, its weight ratio separately is 45: 40: 15, thereby forms cathode agent.Use with the 2mg mixture at 2 tons/cm 2Following press molding is the plate of diameter 2.4mm.After this, negative plate 104 usefulness that so obtain are contained with carbon the electrode current collector 2 of the conductive adhesive resin that is electroconductive stuffing, be adhered to integrated on the negative pole housing 105 (negative pole blocking) after, at 250 ℃ of decompression heat dryings 8 hours down.Subsequently, onboard, press to be stained with the lithium paper tinsel 106 that strikes out diameter 2.4mm, thick 0.25mm, form lithium-negative plate lamination electrode.
After being the nonwoven fabrics drying that forms of the glass fibre of 0.2mm by thickness, strike out φ 3mm, form dividing plate 109.Packing ring 108 uses the material that is made by PPS.In electrolyte 107, use at ethylene carbonate (EC): (volume ratio of γ-BL) is to be dissolved with 1 mol LiBF4 (LiBF in 1: 1 the mixed solvent to gamma-butyrolacton 4) solution, 6 these solution of μ L are injected in the battery tank body.By with the stacked preparation battery that seals of positive pole unit and negative pole unit.
For about 10 batteries,,, carried out reflux test in 1 minute 240 ℃ of heating by 180 ℃ of preheatings 5 minutes in order to investigate the tolerance of battery under reflux temperature by above-mentioned preparation.Sample after the heating carries out the mensuration of cell height, the mensuration of internal resistance, the mensuration of cycle characteristics in order to investigate its dilatancy.Height is measured with amesdial.Internal resistance is measured by alternating current method (1kHz).The condition that discharges and recharges in cycle characteristics, charging are that 0.05mA, constant voltage value are 2.5V, charging interval to be that 20 hours constant current constant voltage mode is carried out with maximum current, and the constant current, the final voltage that discharge at 0.025mA are to carry out under the 0.7V.Figure 6 shows that, when the cycle characteristics of the battery of embodiment 4 is measured, the charging and discharging curve of the 2nd circulation.Discharge capacity demonstrates when 1V and is 0.5mAh, and the result is good.
The expansion of battery all below 0.03mm, is no problem level.Internal resistance also is no problem level in positive and negative 20% before the testing behind reflux test.What discharge and recharge the results are shown among Fig. 6.
According to the method identical, with Si, WO with embodiment 4 2, WO 3Prepare battery as negative electrode active material.Equally, the expansion of battery below 0.03mm, is a level out of question all.For internal resistance, behind reflux test,, also be no problem level in positive and negative 20% before the test.
The effect of invention
According to above detailed description, the present invention can provide charge/discharge cycle characteristics good by using positive active material as using the material that contains Si in niobium oxide, the negative pole, adapts to the battery of the various lower voltages requirements of machine.

Claims (17)

1, rechargeable nonaqueous electrolytic battery, it is characterized in that, have positive pole, negative pole, nonaqueous solvents, containing in the nonaqueous electrolyte battery of electrolyte, dividing plate and the packing ring of supporting salt, contained positive active material comprises niobium oxide in the described positive pole, and contained negative electrode active material comprises the material that contains Si or W in the described negative pole.
2, according to the rechargeable nonaqueous electrolytic battery of record in the claim 1, it is characterized in that, to containing the described positive pole that contains the anode mixture of niobium oxide or contain described niobium oxide, more than 200 ℃, heat-treat below 300 ℃.
3, according to the rechargeable nonaqueous electrolytic battery of record in the claim 1, it is characterized in that described niobium oxide is Nb 2O 5
4, according to the rechargeable nonaqueous electrolytic battery of record in the claim 3, it is characterized in that described niobium oxide is to heat-treat the Nb that obtains under the temperature below 900 ℃ more than 600 ℃ 2O 5
5, according to the rechargeable nonaqueous electrolytic battery of record in the claim 3, it is characterized in that described Nb 2O 5Be to contain oxidation price ratio Nb 2O 5The niobium oxide of low niobium heats generation under the temperature below 900 ℃ more than 600 ℃.
6, according to the rechargeable nonaqueous electrolytic battery of record in the claim 5, it is characterized in that, contain the described Nb of oxidation price ratio 2O 5The niobium oxide of low niobium is NbO or NbO 2
According to the rechargeable nonaqueous electrolytic battery of record in the claim 3, it is characterized in that 7, described niobium oxide is that niobic acid is heated the Nb that generates under the temperature below 900 ℃ more than 600 ℃ 2O 5
8, according to the rechargeable nonaqueous electrolytic battery of record in the claim 7, it is characterized in that it is water miscible containing adhesive contained in the anode mixture of described niobium oxide.
According to the rechargeable nonaqueous electrolytic battery of record in the claim 1, it is characterized in that 9, described negative electrode active material is the active material that is selected among SiO and the Si more than one.
10, according to the rechargeable nonaqueous electrolytic battery of record in the claim 9, it is characterized in that described negative electrode active material is SiO.
11, according to the rechargeable nonaqueous electrolytic battery of record in the claim 10, it is characterized in that described negative electrode active material is SiO, the composition formula of the Si oxide that contains lithium that can electrochemistry occlusion lithium in described negative electrode active material is with Li xSiO represents that the content x of lithium is 4.0≤X≤4.5.
According to the rechargeable nonaqueous electrolytic battery of record in the claim 3, it is characterized in that 12, described negative electrode active material contains and is selected from WO 2, WO 3, SiO more than one material, the boiling point of described nonaqueous solvents under normal pressure is more than 200 ℃, the heat distortion temperature of described dividing plate is more than 230 ℃, the heat distortion temperature of described packing ring is more than 230 ℃.
13, according to the rechargeable nonaqueous electrolytic battery of record in the claim 12, it is characterized in that described support salt is fluorine-containing.
14, according to the rechargeable nonaqueous electrolytic battery of record in the claim 13, it is characterized in that described support salt is selected from hexafluoro and closes lithium phosphate (LiPF 6), tetrafluoro closes lithium borate (LiBF 4) in separately or compound.
According to the rechargeable nonaqueous electrolytic battery of record in the claim 12, it is characterized in that 15, described nonaqueous solvents is selected from the independent or compound in ethylene carbonate (EC), the gamma-butyrolacton (γ BL).
16, the rechargeable nonaqueous electrolytic battery of putting down in writing in each according to claim 12～15, it is characterized in that, it is resin more than 230 ℃ that described dividing plate contains glass fibre or heat distortion temperature, and described packing ring to contain heat distortion temperature be resin more than 230 ℃.
17, according to the rechargeable nonaqueous electrolytic battery of putting down in writing in the claim 16, it is characterized in that the heat distortion temperature that can be used for described dividing plate or described packing ring is that the resin more than 230 ℃ is polyphenylene sulfide, liquid crystal polymer (LCP), polyether-ether-ketone resin (PEEK), polyethers nitrile resin (PEN), polyamide-imide resin or tetrafluoroethene-perfluoroalkyl vinyl ether copolymer resins.
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CN102326281A (en) * 2009-02-19 2012-01-18 日产自动车株式会社 Electricity storage device electrode and manufacturing method for same
CN103168380A (en) * 2010-10-15 2013-06-19 株式会社大阪钛技术 Powder for lithium ion secondary battery negative pole material, lithium ion secondary battery negative pole and capacitor negative pole, and lithium ion secondary battery and capacitor
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JP2006147159A (en) * 2004-11-16 2006-06-08 Matsushita Electric Ind Co Ltd Nonaqueous electrolyte battery
JP4951207B2 (en) * 2005-02-09 2012-06-13 Ｆｄｋエナジー株式会社 Cylindrical sealed battery
JP2006228515A (en) * 2005-02-16 2006-08-31 Sii Micro Parts Ltd Nonaqueous electrolyte secondary battery
JP7099489B2 (en) * 2020-04-10 2022-07-12 三菱マテリアル株式会社 Negative electrode material, battery, method of manufacturing negative electrode material, and method of manufacturing battery

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CN115053369A (en) * 2021-12-29 2022-09-13 宁德新能源科技有限公司 Electrochemical device and electronic device

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