CN100454610C - Lithium polymer secondary battery and process for producing the same - Google Patents

Lithium polymer secondary battery and process for producing the same Download PDF

Info

Publication number
CN100454610C
CN100454610C CNB038064596A CN03806459A CN100454610C CN 100454610 C CN100454610 C CN 100454610C CN B038064596 A CNB038064596 A CN B038064596A CN 03806459 A CN03806459 A CN 03806459A CN 100454610 C CN100454610 C CN 100454610C
Authority
CN
China
Prior art keywords
secondary battery
polymer secondary
solid electrolytic
lighium polymer
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB038064596A
Other languages
Chinese (zh)
Other versions
CN1643712A (en
Inventor
西村直人
虎太直人
宇井幸一
西岛主明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sharp Corp
Original Assignee
Sharp Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sharp Corp filed Critical Sharp Corp
Publication of CN1643712A publication Critical patent/CN1643712A/en
Application granted granted Critical
Publication of CN100454610C publication Critical patent/CN100454610C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

Lithium polymer secondary batteries employing a solid polymer electrolyte layer obtained through crosslinking with energy such as heat or light have a low discharge capacity at temperatures as low as, e.g., -20 DEG C. It is hence desired to improve the low-temperature characteristics without causing capacity deterioration even when charge-discharge cycling is repeated. The lithium polymer secondary battery comprises: a solid polymer electrolyte layer comprising a separator (excluding nonwoven fabrics) and an organic electrolytic solution united therewith through crosslinking; and a positive electrode and a negative electrode each obtained by uniting the organic electrolytic solution with an active material through crosslinking. This lithium polymer secondary battery has a constitution in which the organic electrolytic solution contains gamma-butyrolactone and the solid polymer electrolyte layer has a light transmittance of 50% or higher.

Description

Lighium polymer secondary battery and manufacture method thereof
Technical field
The invention relates to lighium polymer secondary battery and manufacture method thereof.In more detail, the invention relates to charge and low-temperature characteristics than previous more remarkable lighium polymer secondary battery and manufacture method thereof.
Background technology
Be accompanied by the power supply that IT development of technology lithium rechargeable battery is used as mobile phone, portable information terminal, subnotebook PC etc. in a large number.
In recent years, substitute the organic electrolyte of lithium rechargeable battery and use the exploitation of the lighium polymer secondary battery of solid electrolyte layer carrying out energetically, and use organic electrolyte by high molecular physical crosslinking and the lighium polymer secondary battery that is called as Bellcore (ベ Le コ ア) type of the solid electrolyte layer of matrixization existing sale on market.
Yet the lighium polymer secondary battery that utilizes physical crosslinking is separated in the matrix of solid electrolyte layer under hot environment or during the abnormal heating of battery, and the possibility that organic electrolyte oozes out is very high, thus aspect the reliability of battery still residual problem.Moreover the lighium polymer secondary battery that is separated is when carrying out charge and discharge cycles repeatedly, and the phenomenon that rapid capacitance reduces then might take place suddenly, and cycle characteristics also has problems.
Therefore opposite with physical crosslinking, developing and using the crosslinked lighium polymer secondary battery that makes the polymeric solid electrolytic layer of organic electrolyte matrixization that utilizes by chemical bond.This polymeric solid electrolytic layer is with having mixed crosslinked preceding precursor with at least 1 or 1 above unsaturated double-bond and the solution that contains the organic electrolyte of lithium salts, by the product of heat and light equal energy source crosslinked (polymerization).Therefore, in case crosslinked polymeric solid electrolytic layer is separated even matrix is rare under the hot environment or during the abnormal heating of battery.So reliability is very high, be expected to as the also superior lighium polymer secondary battery of charge.
Use is by heat and light equal energy source and the lighium polymer secondary battery of the crosslinked polymeric solid electrolytic layer that obtains, although also being difficult to take place under the hot environment or during the abnormal heating of battery spills etc. because of liquid oozes out liquid, have when carrying out charge and discharge cycles repeatedly the advantage that rapid capacitance reduces does not take place.But because polymeric solid electrolytic layer forms firm reticulated structure with chemical crosslinking, so utilize the degree of excursion step-down of the lighium polymer secondary battery ion of physical crosslinking, the problem of still residual discharge capacity step-down under-20 ℃ of such low temperature particularly.
Moreover lighium polymer secondary battery is to insert polymeric solid electrolytic layer as dielectric substrate between positive pole and negative pole, but because this dielectric substrate is the matrix that contains organic electrolyte, so the intensity of prevention internal short-circuit of battery and inadequate.Therefore, generally be to make dividing plate and organic electrolysis liquid integrated and use as polymeric solid electrolytic layer.Yet when using dividing plate, for example by under the crosslinked situation of wishing to get polymeric solid electrolytic layer such as ultraviolet irradiation, the problem of existence is, this light is covered because of dividing plate, thereby the crosslinked reliability that will become insufficient infringement battery.
In addition, for example open the technology that discloses the degree of in battery, utilizing optical transmission rate measurement polymer dielectric phase change in the flat 9-7577 communique in the spy; Application in the technology of the modulation standard of the raw material when disclosing the material with carbon element that utilizes the optical transmission rate to judge the manufacturing negative electrode for lithium secondary battery in the flat 11-121003 communique of Yu Tekai.But the performance of improving the polymeric solid electrolytic layer of lighium polymer secondary battery is relevant to the situation of light transmittance application usually and is not clearly disclosed so far.
Summary of the invention
The present invention is the achievement of making in view of above-mentioned problem, and its purpose is to provide does not damage charge but the lighium polymer secondary battery and the manufacture method thereof of low-temperature characteristics brilliance.
Particularly according to the invention provides a kind of lighium polymer secondary battery, it is characterized in that, this battery comprises: contain high molecular positive pole and negative pole crosslinked in the presence of organic electrolyte and active material, and between the two poles of the earth, and contain high molecular polymeric solid electrolytic layer crosslinked under the existence of organic electrolyte and dividing plate (not containing adhesive-bonded fabric), above-mentioned organic electrolyte contains gamma-butyrolacton, and above-mentioned polymeric solid electrolytic layer has the light transmittance more than 50% or 50%.
Moreover, according to the present invention, a kind of manufacture method of lighium polymer secondary battery is provided, this method is to make the method for above-mentioned lighium polymer secondary battery, it is characterized in that, comprise be adjusted at organic electrolyte and crosslinked before the light transmittance of high molecular existence dividing plate down become more than 50% or 50% after, make crosslinked preceding macromolecule crosslinked and obtain the step of polymeric solid electrolytic layer.
The simple declaration of accompanying drawing
Fig. 1 is the summary section of lighium polymer secondary battery of the present invention.
The working of an invention scheme
In the present invention, one of its feature is when the manufacturing of polymeric solid electrolytic layer, with organic electrolyte and crosslinked before the light transmittance adjustment of the dividing plate of macromolecule under existing become more than 50% or 50%.By measuring light transmittance, assert on the dividing plate that whether fully infiltration has mixed crosslinked preceding precursor (hereinafter to be referred as precursor) and contained the solution of the organic electrolyte of lithium salts.
Among the present invention,, then can make easy and high performance lighium polymer secondary battery by light transmittance being modulated into more than 50% or 50%.
Light transmittance is that this illumination across dividing plate is measured in the ultraviolet ray of for example illumination wavelength 365nm on object, and can calculate according to following formula.
Not light transmittance=(across the illumination of the dividing plate)/illumination of dividing plate (not every) * 100 (%)
Dividing plate is white before the solution impregnation, and the transmitance of light is roughly 0%, however become during impregnation solution translucent～transparent.Therefore, can make the impregnation degree quantification of solution with the transmitance of light according to above-mentioned formula to dividing plate.At this moment, transmitance is inadequate to the impregnation of dividing plate less than 50% o'clock solution, not only improves the internal resistance of battery, so and insufficient undesirable with the cross-linking reaction under the situation of photo-crosslinking.Comparatively ideal light transmittance is more than 60% or 60%, and better is more than 70% or 70%, is desirably especially more than 80% or 80%, is desirably most more than 90% or 90%.(on be limited to 100%)
Moreover, because of in the light transmittance of crosslinked back polymeric solid electrolytic layer with crosslinked before the light transmittance of dividing plate roughly hang down 1～2% on an equal basis or approximately, also can so after crosslinked, measure.In addition, if measure, just can select to be only limited to the polymeric solid electrolytic layer of advantageous characteristic in advance in crosslinked back.
Fig. 1 illustrates the overview profile of lighium polymer secondary battery one example of the present invention.Among Fig. 11 is dividing plate, the 2nd, polymeric solid electrolytic layer, the 3rd, positive active material, the 4th, negative electrode active material, the 5th, collector body.
If beyond the dividing plate adhesive-bonded fabric in the polymeric solid electrolytic layer among the present invention, then be not particularly limited, can use known dividing plate.
The ideal thickness of dividing plate be 5～30 μ m, that desirable especially is 8～25 μ m.Mechanical strength step-down when thinner than 5 μ m is so the positive pole of battery and negative pole have the situation of short circuit undesirable.But the impedance of the elongated not only inside battery of interelectrode distance uprises when thicker than 30 μ m, and have impregnation to mix precursor and the situation of the light transmittance step-down when containing the solution of organic electrolyte of lithium salts with at least 1 or 1 above unsaturated double-bond, so undesirable.
In addition, can enumerate microporous membrane etc. as dividing plate.As dividing plate, available adhesive-bonded fabric, however its diameter than the pore of microporous membrane is big, and positive pole and/or negative electrode active material run through adhesive-bonded fabric, and the possibility of the short circuit of generation battery is very high.Therefore, use microporous membrane to be ideal.Particularly microporous membrane intensity and the cost aspect that is made of the polyolefin that contains polyethylene, polypropylene or polyethylene and polyacrylic compound is desirable.Here, so-called microporous membrane is meant that the hole that contains 0.01～10 μ m is 10 2～10 12Individual/cm 2Film.
Moreover under the situation of the solvent that is difficult to permeate in the TPO film that uses gamma-butyrolacton (GBL) and so on, the solvent compatibility person who improves film is desirable.As the raising method, can enumerate method, with method of surfactant coated film etc., yet be not limited to these with the surface of oxygen plasma treatment film.
The organic electrolyte of the polymeric solid electrolytic layer among the present invention is to use the solution that has dissolved lithium salts in containing the organic solvent of GBL with the concentration of regulation.Amount of moisture in the organic electrolyte is that 50ppm or 50ppm are following for desirable, it is desirable to 20ppm especially or below the 20ppm.Amount of moisture for a long time, when making battery charge, because of the electrolysis of water takes place, efficiency for charge-discharge is low and undesirable.
Lithium salt is that 0.5～2.5mol/l is for desirable.When concentration ratio 0.5mol/l hanged down, so the concentration step-down of the electric charge of polymeric solid electrolytic layer had situation that the impedance of inside battery uprises for desirable.When concentration ratio 2.5mol/l is high, lithium ion and anionic bonding again take place, so the situation that ionic conductance impedance low, that inside battery is arranged uprises is not for desirable.
The kind of lithium salts is not particularly limited, and can use LiPF 6, LiBF 4, LiN (CF 3SO 2) 2Deng.
The GBL of the neccessary composition in the organic solvent, containing more than 60% or 60% in volume ratio with respect to other solvents is ideal.GBL is than 60% after a little while, and because of ionic conductance step-down under-20 ℃ low temperature, the low-temperature characteristics of battery worsens so be ideal.As other solvent, can enumerate for example cyclic carbonates of propylene carbonate (PC), ethylene carbonate (EC) etc., the linear carbonate class of diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC) etc., the ring-type ethers of oxolane, 2-methyltetrahydrofuran etc., the chain ethers of Anaesthetie Ether, dimethoxy-ethane, diethoxyethane, ethyoxyl methoxy base ethane etc., ester classes such as methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, other acetonitrile, sulfolane, N-N-methyl-2-2-pyrrolidone N-etc. are arranged.These solvents also can use multiple.
More particularly, for example,,, do not make efficiency for charge-discharge lowly can improve low-temperature characteristics, so suitable because of in GBL, having mixed the solvent of EC using under the situation of graphite based material in negative electrode active material yet.Particularly the volume ratio of GBL: EC be 60: 40～80: 20 for desirable.GBL become than 60: 40 after a little while, the ionic conductance step-down under-20 ℃ the low temperature, so the performance of battery also has the situation of step-down for desirable.And that GBL becomes when higher than 80: 20 the efficiency for charge-discharge of battery is low, and so the situation of deterioration that battery capacity takes place when carrying out charge and discharge cycles repeatedly is for desirable.
As the preceding macromolecule (precursor) of polymeric solid electrolytic layer crosslinked (polymerization); be random copolymer or the block polymer that molecule includes ethylene oxide unit and propylene oxide units, the multi-functional compounds who has unsaturated bonds such as acryloyl group or methacryl at its end is for desirable.Even it is because also can be crosslinked with end under the existence of the high solvent of the solvabilities such as macromolecule of GBL and so on.In addition, have the precursor of monofunctional and the precursor of multiple functional radical, can make the solid electrolyte layer of crosslinked configuration of all kinds by mixing.
Precursor for the amount of the organic electrolyte that contains lithium salts is precursor: the weight ratio of organic electrolyte be 7: 93～3: 97 for desirable.The quantitative change of precursor be than 7: 93 for a long time, so the situation of ionic conductance step-down that promptly has polymeric solid electrolytic layer is for desirable.And the amount of precursor than 3: 97 after a little while, promptly have situation that cross-linking reaction can not fully finish so for desirable.
Crosslinked for promoting (polymerization) reaction also can be used initator.As the initator that is begun to react by luminous energy, the phosphine oxide of can giving an example (Off オ ス Off イ Application オ キ シ De) is, acetyl benzene series, benzophenone series, alpha-alcohol ketone system, michler's ketone system, benzil (ベ Application ジ Le) are, benzoin system, benzoin ether system, benzyl methyl ketal based compound etc.These initators can a kind or also can mix more than 2 kinds or 2 kinds and use.
As the initator that begins to react by heat energy, the organic peroxide based compound is suitable.As its concrete example; the isobutyl group hydrogen peroxide of can giving an example; α; α '-two (new capryl peroxidating) diisopropyl benzene; the cumenyl new decanoate ester peroxide; two-n-propyl group peroxy dicarbonate; diisopropyl peroxydicarbonate; 1; 1; 3,3-tetramethyl butyl new decanoate ester peroxide; two (4-t-butyl cyclohexyl) peroxy dicarbonate; 1-cyclohexyl-1-Methylethyl new decanoate ester peroxide; two-2-ethoxyethyl group peroxy dicarbonate; two (peroxidating of 2-ethylhexyl), two carbonic esters; t-hexyl new decanoate ester peroxide; dimethoxy butyl peroxyization two carbonic esters; two (3-methyl-3-methoxyl group butyl peroxyization), two carbonic esters; t-butyl peroxy neodecanoic acid ester; the special pentyl ester of t-peroxidating etc.These initators can a kind or mix more than 2 kinds or 2 kinds and use.
These initators with respect to precursor and the total weight that contains the solution that the organic electrolyte of lithium salts mixes be that the ratio of 100～5000ppm is added to ideal.
As the autofrettage of concrete polymeric solid electrolytic layer, the solution (also adding initator according to situation) that at first will mix precursor and contain the organic electrolyte of lithium salts contains in advance and is dipped in the dividing plate.Secondly, with under the situation of photo-crosslinking, press 5～500mW/cm with the light of wavelength 300～800nm scope 2Illumination irradiation 1～1200 second, and under the situation with heat cross-linking, 30～80 ℃ of following heat treatments 0.5～100 hour and the manufacturing polymeric solid electrolytic layer.
In photo-crosslinking, wavelength becomes than 300nm in short-term, has the situation that precursor itself decomposes and lithium salts decomposes to take place so be not desirable.But when becoming, there is cross-linking reaction to become inadequate situation so also for desirable than 800nm length.So in heat cross-linking, temperature becomes when lower than 30 ℃, promptly has cross-linking reaction to become inadequate situation for desirable.And become when higher than 80 ℃, so the situation of decomposition that volatilization that organic solvent contained in this solution takes place and lithium salts are arranged is also for desirable.
Polymeric solid electrolytic layer among the present invention is the product that impregnation or maintenance contain the organic electrolyte of lithium salts.Layer like this sees it is solid state on macroscopic view, yet sees it is that lithium salt solution forms continuous phase on microcosmic, also shows the ionic conductance higher than the polymeric solid electrolytic layer that does not use solvent.
As positive active material, be not particularly limited, can use well known in the art any.For example among the present invention, can use the metal oxide that contains lithium as positive active material.Particularly from Li a(A) b(B) cO 2(in this, A is the element more than a kind or 2 kinds or 2 kinds in the transition metal.B is from the nonmetalloid of periodic table IIIB, IVB and VB family and metalloid element, alkaline earth metalloid, Zn, Cu, the element of selecting among the metallic elements such as Ti more than a kind or 2 kinds or 2 kinds.A, b, c are respectively do for oneself 0＜a≤1.15,0.85≤b+c≤1.30,0＜c.) composite oxides or contain of bedded structure of expression select in the composite oxides of spinelle structure at least a kind are for desirable.In addition, these metal oxides are ideal because of the effect event that also has the reaction that promotes the organic peroxide thermal polymerization.
As the representational composite oxides LiCoO that can give an example 2, LiNiO 2, LiCo xNi 1-xO 2(0＜x＜1) etc.These composite oxides use the situation of carbonaceous material in negative electrode active material, have the following advantages:
(1) even follows change in voltage (about 1Vvs.Li/Li of the charging and discharging of carbonaceous material itself +) the practical operating voltage of also demonstration abundance,
(2) the necessary lithium ion of the charging and discharging of battery reaction is before assembled battery, with for example LiCoO 2, LiNiO 2Be contained in the battery etc. form.
As negative electrode active material, be not particularly limited, can use arbitrary known material in this area.For example, can use carbonaceous material as negative electrode active material.Carbonaceous material is the material of insertion/disengaging lithium gained on the electrochemistry preferably.The current potential of insertion/disengaging lithium approaches separating out/dissolution potential of lithium metal, so can constitute the battery of high-energy source density.Its typical case is the natural or Delanium of particle shape (flakey, bulk, fibrous, whisker shape, spherical, sized particles shape etc.).Use with meso carbon microballon grain, mesophase pitch powder, etc. the Delanium that obtains of graphitizations such as tropism's asphalt powder also can.
As comparatively ideal carbonaceous material, can be schematically illustrated in the graphite particle of surface attachment amorphous carbon.As the method for adhering to is to be in the mink cell focus and to mention by the oil that graphite particle is impregnated into coal measures heavy oil such as tar, pitch or heavy oil etc., is heated to that carburizing temperature is above decomposes mink cell focus and obtain again.Moreover, also can pulverize the carbonaceous material that obtains as required.By processing like this, prevent the organic solvent that takes place in negative pole because of when charging and the decomposition reaction of lithium salts wittingly, thus improved charge and discharge circulation life, and can prevent the generation of the gas that causes owing to this decomposition reaction.
In addition, carbonaceous material is with the relevant pore of measuring according to the BET method of specific area, owing to there being certain degree to stop up adhering to of amorphous carbon.Concrete specific area is 1～5m 2The scope of/g is desirable.Specific area becomes when bigger than this scope, also becomes greatly with the contact area of the organic electrolyte that has dissolved lithium salts in the organic solvent, so that these decomposition reaction takes place Yin Gengyi is undesirable.In addition, because of increasing to the adsorbance that on negative pole, forms the initator of polymeric solid electrolytic layer, so hinder the crosslinked of precursor so undesirable.And specific area becomes than this scope hour, because of also diminishing with electrolytical contact area, makes the reaction speed on the electrochemistry slack-off, because of the situation of part throttle characteristics step-down that battery is arranged so also undesirable.
Anodal, negative pole be basically with adhesive the active material layer separately of anodal, negative electrode active material, on the metal forming that constitutes collector body, form.As the material of the metal forming that becomes above-mentioned collector body can give an example aluminium, stainless steel, titanium, copper, nickel etc.Wherein, when considering stability, extensibility on the electrochemistry and economy, preferred anodal aluminium foil, the negative pole of using uses Copper Foil.
Moreover, as the positive pole beyond the paper tinsel, the form of negative electrode collector, can be for example at screen cloth, flexible metal, lath body, porous body or on resin film, applied the form of electrically conductive material etc., yet be not limited to these.
Electric conducting material that in case of necessity can graphite, carbon black, acetylene black, electrical conductivity Carbon black, carbon fiber, conductive metal oxide etc. are chemically stable in the manufacturing of positive pole, negative pole and active substance combination are used, and can improve electron conductivity.
In addition, in the manufacturing of anodal, negative pole, adhesive is soluble in chemically stable, the appropriate solvent, but is chosen as ideal among never encroaching on the resin of organic electrolyte.Numerous resins is known, for example optionally is dissolved in the N-methyl-2-pyrrolones (NMP) as organic solvent but is that stable Kynoar (PVDF) preferably is used in organic electrolyte.Moreover, be not dissolved in the adhesive in the solvent, also can be used as dispersion liquid and use.
Other spendable resins, for example can give an example acrylonitrile, methacrylonitrile, PVF, chlorobutadiene, vinylpyridine, styrene butadiene ribber (SBR), carboxymethyl cellulose (CMC) and derivative thereof, vinylidene chloride, ethene, propylene, cyclic diene (for example, cyclopentadiene, 1,3-cyclohexadiene etc.) etc. polymer and copolymer.
Electrode is with active material and electric conducting material in case of necessity is mixing makes paste in the solution of adhesive resin, it is applied on the metal forming with homogeneous thickness with suitable coating machine again, can make by exerting pressure after the drying.The ratio of the adhesive in the electrode is an ideal with the bottom line as necessity, and as 100 weight portions, 1～15 weight portion that is generally is for abundant with electrode.Electric conducting material be with electrode as 100 weight portions, be generally 2～15 weight portions.
Lighium polymer secondary battery of the present invention for example can be made according to following method.
(1) will mix the precursor that contains at least 1 or 1 above unsaturated double-bond in each positive pole, negative pole and the dividing plate impregnation and contain the solution of the organic electrolyte of lithium salts in advance, to each irradiation heat or light or both sides' the energy and carry out the crosslinked product that obtains is made battery by fitting method.
(2) the pre-solution prior to loading dividing plate on arbitrary electrode and another electrode impregnation having been mixed the precursor that contains at least 1 or 1 above unsaturated double-bond and contained the organic electrolyte of lithium salts, the energy that both sides are shone heat or light or both sides carries out the method that crosslinked and applying products therefrom is made battery again.
(3) in advance prior to sandwiching dividing plate between positive pole and the negative pole, and its impregnation mixed the precursor that contains at least 1 or 1 above unsaturated double-bond and contained the solution of the organic electrolyte of lithium salts, the energy that both sides are shone heat or light or both sides carries out the method that crosslinked and applying products therefrom is made battery again.
According to the invention described above, can provide and not damage charge, but aspect low-temperature characteristics the lighium polymer secondary battery of brilliance.
The unit that comprises positive pole, dividing plate and negative pole formation can constitute overlapping or the stack-up type of coiling or convoluted lighium polymer secondary battery.
The battery of making can be used in the product that imposes nickel plating on the iron and aluminum cylindric jar, square jar or can press resin molding as housing material in the aluminium foil upper strata, yet be not limited to these.
These battery manufacturing steps are for the immersion of prevention moisture is preferably being carried out under the inert gas environments such as argon gas and nitrogen or in the air of drying.
Embodiment
Followingly specify the present invention, yet the present invention is not restricted to these embodiment at all according to embodiment.Moreover the capacitance of the battery of manufacturing all becomes 20mAh.
(embodiment 1)
Make the battery of embodiment 1 by following step.
A) Zheng Ji manufacturing
The average grain diameter of mixing 100 weight portions is the LiCoO of 7 μ m 2, 5 weight portions as the acetylene black of electric conducting material and the PVDF as adhesive of 5 weight portions, as solvent add an amount of NMP mixing and the positive electrode paste.With its be applied in pressurize after the drying on the Al paper tinsel of 20 μ m positive wafer thin.Should be cut to 30 * 30mm by positive wafer thin, and welding Al current collection joint ( Block) obtains positive pole.
B) manufacturing of negative pole
(average grain diameter is 12 μ m, and specific area is 2m amorphous carbon to be attached to the material with carbon element powder on the surface of graphite particle 2/ g) 100 weight portions are that 100: 9 ground is mixed with PVDF as adhesive by weight, as solvent add an amount of NMP and carry out mixing and the negative material paste.With its be applied in press after the drying on the Cu paper tinsel of 18 μ m the negative pole thin slice.This negative pole is cut to 30 * 30mm, and welding Ni current collection joint ( Block) obtains negative pole.
C) precursor solution of modulation polymeric solid electrolytic layer
In 80: 20 the volume ratio mixed solvent of GBL and EC, dissolve LiBF 4, making its concentration is 2mol/l, obtains organic electrolyte.
The molecular weight that mixes 3.5 weight % in this 95 weight % organic electrolyte is that the molecular weight of 7500～9000 3 functional polyethers polyalcohol acrylates and 1.5 weight % is 2800～3000 monofunctional polyethers polyalcohol acrylate, again with respect to above-mentioned solution add 2000ppm as 2 of Photoepolymerizationinitiater initiater, 4,6-trimethyl-benzoyloxy phenyl phosphine oxide (2,4,6-ト リ メ チ Le ベ Application ゾ イ Le Off エ ニ Le Off オ ス Off イ Application オ キ シ De) and obtain precursor solution.
D) assembling of battery
On the positive pole of above-mentioned gained, load onto dividing plate (thickness is 24 μ m) with the surface-treated polypropylene system of polyoxy propylene glycol, inject precursor solution.With its clamping, is that the ultraviolet ray of 365nm with 20mW/cm with wavelength with 2 quartz glass plates (thickness 500 μ m) 2 Illumination irradiation 2 minutes.Secondly, in negative pole, inject precursor solution, with positive pole irradiation ultraviolet radiation similarly.Opposed to each other these are fitted with positive pole and negative pole, be inserted in the bag as the aluminium lamination pressurizing resin film system of housing material, with the sealing of heat-sealing material.Making it finish battery in 24 hours 60 ℃ of following heat treated makes.And only the light transmittance of the wavelength 365nm of polymeric solid electrolytic layer is 87% (being 89% before the ultraviolet irradiation).
(embodiment 2)
Make the battery of embodiment 2 with following step.
A) Zheng Ji manufacturing
Repeat operation similarly to Example 1 and obtain positive pole.
B) manufacturing of negative pole
Repeat operation similarly to Example 1 and obtain negative pole.
C) precursor solution of modulation polymeric solid electrolytic layer
In 60: 40 the volume ratio mixed solvent of GBL and EC with LiBF 4Thereby dissolving becomes the concentration of 1mol/l obtains organic electrolyte.
In this organic electrolyte 80 weight %, the molecular weight that mixes 12 weight % is that the molecular weight of 7500～9000 3 functional polyethers polyalcohol acrylates and 8 weight % is 220～300 monofunctional polyethers polyalcohol acrylate, moreover to above-mentioned solution add 3000ppm as two (2 of Photoepolymerizationinitiater initiater, 6-dimethoxy benzoyl)-2,4,4-trimethyl-amyl group phosphine oxide and obtain precursor solution.
D) assembling of battery
On the above-mentioned positive pole that obtains, with the dividing plate (thickness is 9 μ m) of the surface-treated polyethylene system of polyoxyethylene glycol, inject precursor solution on the loading.And with 2 quartz glass plates (thickness is 500 μ m) with its clamping, be that the ultraviolet ray of 365nm is with 20mW/cm with wavelength 2Illumination irradiation 2 minutes.Next injects precursor solution and similarly carries out ultraviolet irradiation with positive pole in negative pole.With positive pole and negative pole opposed to each other with these applyings and be inserted in the bag as the aluminium foil laminate resin molding system of housing material, with the sealing of heat-sealing material.Under 80 ℃, be heated to handle to make in 2 hours and finish the battery making.And only the light transmittance of the wavelength 365nm of polymeric solid electrolytic layer is 92% (being 93% before the ultraviolet irradiation).
(embodiment 3)
Make the battery of embodiment 3 by following step.
A) Zheng Ji manufacturing
Repeat operation similarly to Example 1 and obtain positive pole.
B) manufacturing of negative pole
Be that 100: 9 ground mixes 100 weight portion Delanium powder (average grain diameter is 12 μ m, and specific area is 5m by weight 2/ g) and as the PVDF of adhesive, add an amount of NMP as solvent and carry out the mixing negative material paste that obtains.It is applied in the pressurization of dry back obtains the negative pole thin slice on the Cu paper tinsel of 18 μ m.This negative pole shearing of thin disc is become 30 * 30mm, and welding Ni current collection joint ( Block) obtains negative pole.
C) precursor solution of modulation polymeric solid electrolytic layer
In 75: 25 volume ratio mixed solvents of GBL and EC, dissolve LiBF 4And to make its concentration be that 0.8mol/l obtains organic electrolyte.
The molecular weight that mixes 2.4 weight % in this organic electrolyte 97 weight % is that the molecular weight of 7500～9000 3 functional polyethers polyalcohol acrylates and 0.6 weight % is 220～300 monofunctional polyethers polyalcohol acrylate, obtains precursor solution to what above-mentioned solution added 1000ppm as the t-butyl peroxy neodecanoic acid ester of thermal polymerization again.
D) assembling of battery
Between the above-mentioned negative pole and positive pole that obtains, the dividing plate of clamping oxygen plasma surface-treated polyethylene system (thickness 13 μ m), and these are inserted in the bag as the aluminium foil laminate resin molding system of housing material, and flow into c) in this bag of sealing behind the precursor solution that obtains.Under 60 ℃, be heated to handle and made the making of finishing battery in 72 hours.And only measure the light transmittance of the wavelength 760nm of polymeric solid electrolytic layer.Light transmittance is 59% (being 60% before the heating).
(comparative example 1)
Make the battery of comparative example 1 by following step.
A) Zheng Ji manufacturing
Repeat operation similarly to Example 1 and obtain positive pole.
B) manufacturing of negative pole
Repeat operation similarly to Example 1 and obtain positive pole.
C) precursor solution of modulation polymeric solid electrolytic layer
In 30: 70 volume ratio mixed solvents of EC and DMC, dissolve LiBF 4, and to make its concentration be that 1.5mol/l obtains organic electrolyte.
Other repeat operation similarly to Example 1 and obtain precursor solution.
D) assembling of battery
On the above-mentioned positive pole that obtains, put the dividing plate (thickness 24 μ m) of polypropylene system, inject precursor solution.With its clamping, is that the ultraviolet ray of 365nm with 20mW/cm with wavelength with 2 quartz glass plates (thickness 500 μ m) 2 Illumination irradiation 2 minutes.Secondly, the injection precursor solution reaches with positive pole and similarly uses ultraviolet irradiation in negative pole.They are fitted opposed to each other with positive pole and negative pole and be inserted in the bag as the aluminium foil laminate resin molding system of housing material,, under 60 ℃, be heated to handle and made battery finish making in 24 hours with the sealing of heat-sealing material.And only the light transmittance of the wavelength 365nm of polymeric solid electrolytic layer is 80% (being 82% before the heating).
(comparative example 2)
Make the battery of comparative example 2 by following step.
A) Zheng Ji manufacturing
Repeat operation similarly to Example 1 and obtain positive pole.
B) manufacturing of negative pole
Repeat operation similarly to Example 1 and obtain positive pole.
C) precursor solution of polymeric solid electrolytic layer modulation
Repeat operation similarly to Example 1 and obtain precursor solution.
D) assembling of battery
On the above-mentioned positive pole that obtains, put the dividing plate (thickness 30 μ m) of polypropylene system, inject precursor solution.Other repeat operation similarly to Example 1 and make the making of finishing battery.And only the light transmittance of the wavelength 365nm of polymeric solid electrolytic layer is 48% (being 49% before the ultraviolet irradiation).
(comparative example 3)
Make the battery of comparative example 3 by following step.
A) Zheng Ji manufacturing
Repeat operation similarly to Example 1 and obtain positive pole.
B) manufacturing of negative pole
Repeat operation similarly to Example 1 and obtain positive pole.
C) precursor solution of modulation polymeric solid electrolytic layer
Repeat operation similarly to Example 1 and obtain precursor solution.
D) assembling of battery
On the above-mentioned positive pole that obtains, put the adhesive-bonded fabric (thickness 40 μ m) of polyester, inject precursor solution.Other repeat operation similarly to Example 1 and battery are finished.And only the light transmittance of the wavelength 365nm of polymeric solid electrolytic layer is 73% (being 75% before the ultraviolet irradiation).
Till each battery of above-mentioned manufacturing charged to 4.2V with constant current 4mA, arrive behind the 4.2V with constant-potential charge until current attenuation to 1mA (hereinafter referred to as the 0.2C charging), measure with constant current 20mA 25 ℃ and-20 ℃ till 3V the low temperature electric capacity sustainment rate during discharge and 25 ℃ till 500 times the 0.2C charging and with constant current 20mA reignition the circulation sustainment rate during to 3V.These define with following formulate.
Low temperature electric capacity sustainment rate (%)=(20 ℃ discharge capacity)/(25 ℃ discharge capacity) * 100
Circulation sustainment rate (%)=(the 500th discharge capacity)/(first discharge capacity) * 100
The result of the foregoing description and comparative example shown in the following table 1.
Table 1
Light transmittance (%) Low temperature capacitance sustainment rate (%) Circulation sustainment rate (%)
Embodiment 1 87 68 80
Embodiment 2 92 50 86
Embodiment 3 59 38 88
Comparative example 1 80 3 82
Comparative example 2 48 9 38
Comparative example 3 73 55 33
As shown in table 1, from the result of embodiment 1 and comparative example 1 as can be known, keep the cycle characteristics and the low-temperature characteristics of battery for raising,, also be necessary to use the fact of the polymeric solid electrolytic layer that contains GBL even the light transmittance of polymeric solid electrolytic layer is more than 50% or 50%.
And from the result of embodiment 1 and comparative example 2 as can be known, the light transmittance of polymeric solid electrolytic layer is less than 50% o'clock, the fact that the low-temperature characteristics of battery and cycle characteristics are all low.
Moreover, from the result of embodiment 1 and comparative example 3 as can be known,, be not dividing plate but adhesive-bonded fabric then causes the short circuit of inside battery even light transmittance is more than 50% or 50%, can not keep the fact of cycle characteristics.
Can provide according to the present invention and can keep superior cycle characteristics and can under-20 ℃ of such low temperature, the lighium polymer secondary battery of mis-behave not take place again yet.
In addition, also measuring polymeric solid electrolytic layer crosslinked preceding macromolecule and gamma-butyrolacton with light transmittance as can be known is easy and the fact of the manufacture method of high performance lighium polymer secondary battery to the infiltrative manufacture method of dividing plate.

Claims (8)

1. lighium polymer secondary battery; this battery comprises: positive pole and negative pole; and polymeric solid electrolytic layer; this positive pole and negative pole contain macromolecule crosslinked in the presence of organic electrolyte and active material; and polymeric solid electrolytic layer is between the two poles of the earth; and contain macromolecule crosslinked in the presence of organic electrolyte and dividing plate; described dividing plate does not comprise adhesive-bonded fabric; wherein above-mentioned organic electrolyte contains gamma-butyrolacton; and above-mentioned polymeric solid electrolytic layer has the light transmittance more than 50% or 50%; aforementioned barriers is to comprise polyethylene; the microporous membrane of polypropylene or polyethylene and polyacrylic compound; contained macromolecule is random copolymer or the block copolymer that molecule includes ethylene oxide unit and propylene oxide units in the above-mentioned polymeric solid electrolytic layer; and be to make to comprise multi-functional compounds's the product of precursor polymeric that its end has the unsaturated bond of acryloyl group or methacryl; and above-mentioned negative pole contains carbonaceous material, and this carbonaceous material has 1～5m 2The specific area of/g according to BET method mensuration.
2. according to the described lighium polymer secondary battery of claim 1, wherein above-mentioned organic electrolyte also contains ethylene carbonate, and gamma-butyrolacton: the volume ratio of ethylene carbonate is 60: 40～80: 20.
3. according to the described lighium polymer secondary battery of claim 1, wherein microporous membrane is that the hole of containing 0.01～10 μ m is 10 2～10 12Individual/cm 2Film.
4. according to the described lighium polymer secondary battery of claim 1, its median septum has the thickness of 5～30 μ m.
5. according to the described lighium polymer secondary battery of claim 1, its median septum is the TPO film of film surface with oxygen plasma treatment.
6. according to the described lighium polymer secondary battery of claim 1, its median septum is the TPO film that handle with surfactant on the film surface.
7. the manufacture method of a lighium polymer secondary battery, this method is to make the method for each described lighium polymer secondary battery in the claim 1～6, it is characterized in that, this method comprise organic electrolyte and crosslinked before high molecular in the presence of the light transmittance adjustment of dividing plate reach more than 50% or 50% after, make crosslinked preceding macromolecule crosslinked and obtain the step of polymeric solid electrolytic layer.
8. according to the manufacture method of the described lighium polymer secondary battery of claim 7, wherein above-mentioned light transmittance is to measure with the light of the wavelength of 300～800nm scope.
CNB038064596A 2002-06-19 2003-03-14 Lithium polymer secondary battery and process for producing the same Expired - Fee Related CN100454610C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002178589 2002-06-19
JP178589/2002 2002-06-19

Publications (2)

Publication Number Publication Date
CN1643712A CN1643712A (en) 2005-07-20
CN100454610C true CN100454610C (en) 2009-01-21

Family

ID=29996529

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB038064596A Expired - Fee Related CN100454610C (en) 2002-06-19 2003-03-14 Lithium polymer secondary battery and process for producing the same

Country Status (3)

Country Link
CN (1) CN100454610C (en)
TW (1) TWI222232B (en)
WO (1) WO2004001878A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0607542D0 (en) 2006-04-13 2006-05-24 Thermo Finnigan Llc Mass spectrometer
KR20200044807A (en) * 2017-08-31 2020-04-29 니폰 제온 가부시키가이샤 Composition for electrochemical device functional layer, functional layer for electrochemical device, and electrochemical device
CN108598562B (en) * 2018-03-27 2022-02-01 电子科技大学 Heat treatment method of solid electrolyte film and lithium battery cell structure
CN113629353A (en) * 2021-08-05 2021-11-09 中国科学院近代物理研究所 PET (polyethylene terephthalate) basic weight ion track composite diaphragm for lithium ion battery and preparation method of PET basic weight ion track composite diaphragm

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000106212A (en) * 1998-09-28 2000-04-11 Yuasa Corp Lithium battery
JP2001110244A (en) * 1999-10-12 2001-04-20 Sony Corp Battery cable
WO2001097316A1 (en) * 2000-06-15 2001-12-20 Accentus Plc A cell incorporating a porous membrane

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3650517B2 (en) * 1996-12-03 2005-05-18 三井化学株式会社 Gel polymer solid electrolyte
JPH11288738A (en) * 1998-04-01 1999-10-19 Ricoh Co Ltd Solid electrolytic battery and its manufacture
JP2000228221A (en) * 1998-11-30 2000-08-15 Sanyo Electric Co Ltd Polymer electrolyte battery and manufacture thereof
JP4379966B2 (en) * 1999-08-27 2009-12-09 株式会社ジーエス・ユアサコーポレーション Lithium battery
JP4563555B2 (en) * 2000-07-04 2010-10-13 シャープ株式会社 Lithium secondary battery
JP2002329529A (en) * 2000-09-06 2002-11-15 Toshiba Corp Nonaqueous electrolyte secondary battery
JP2002110243A (en) * 2000-09-29 2002-04-12 Pionics Co Ltd Lithium secondary battery
JP2002110244A (en) * 2000-09-29 2002-04-12 Pionics Co Ltd Lithium secondary battery
JP2002158038A (en) * 2000-11-17 2002-05-31 Sharp Corp Lithium secondary battery
JP4909466B2 (en) * 2001-04-13 2012-04-04 シャープ株式会社 Polymer secondary battery
JP4014816B2 (en) * 2001-04-13 2007-11-28 シャープ株式会社 Lithium polymer secondary battery
JP4027615B2 (en) * 2001-04-20 2007-12-26 シャープ株式会社 Lithium polymer secondary battery
JP2002367677A (en) * 2001-06-05 2002-12-20 Toshiba Battery Co Ltd Manufacturing method of non-aqueous secondary battery
JP3976529B2 (en) * 2001-09-18 2007-09-19 シャープ株式会社 Lithium polymer secondary battery and manufacturing method thereof
JP2003109665A (en) * 2001-09-28 2003-04-11 Sanyo Electric Co Ltd Polymer battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000106212A (en) * 1998-09-28 2000-04-11 Yuasa Corp Lithium battery
JP2001110244A (en) * 1999-10-12 2001-04-20 Sony Corp Battery cable
WO2001097316A1 (en) * 2000-06-15 2001-12-20 Accentus Plc A cell incorporating a porous membrane

Also Published As

Publication number Publication date
TW200404377A (en) 2004-03-16
TWI222232B (en) 2004-10-11
WO2004001878A1 (en) 2003-12-31
CN1643712A (en) 2005-07-20

Similar Documents

Publication Publication Date Title
CN1149700C (en) Solid electrolytic secondary battery
CN103779572B (en) A kind of lithium ion battery negative additive and preparation method thereof, anode plate for lithium ionic cell and lithium ion battery
CN1274052C (en) Method for producing lithium ion secondary cell
CN1310371C (en) Lithium polymer secondary cell
CN1202587C (en) Lighium polymer secondary battery and its production method
CN1930703A (en) Separator coated with electrolyte-miscible polymer and electrochemical device using the same
CN1151578C (en) solid electrolytic secondary battery
CN107342421A (en) A kind of high content pyridine N doping porous carbon negative material, preparation method and applications
CN101615674B (en) Anode active material and secondary battery
CN1235296C (en) Thin secondary battery
CN108780926A (en) The method for preparing secondary cell
JP4945054B2 (en) Lithium polymer secondary battery and manufacturing method thereof
CN1577943A (en) Electrolyte and battery using the same electrolyte
CN1210831C (en) Lithium secondary cell
JP2007157388A (en) Nonaqueous electrolyte secondary battery
CN100454610C (en) Lithium polymer secondary battery and process for producing the same
CN107017397A (en) Graphite composite material and application thereof, preparation method and lithium ion battery
CN1967926A (en) A lithium ion battery and its preparing method
CN1210832C (en) Lithium polymer secondary battery
JP3664560B2 (en) Lithium secondary battery
KR101156537B1 (en) Lithium polymer battery
JP3618022B2 (en) Electric double layer capacitor and EL element
CN117343668A (en) Self-healing ion-electron integrated adhesive and preparation method thereof
CN113764723A (en) Polymer electrolyte, polymer electrolyte layer, and all-solid-state lithium ion battery
CN117673457A (en) Solid-state battery and secondary polymerization preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20090121

Termination date: 20160314