WO2011069331A1 - Batterie lithium-ion - Google Patents

Batterie lithium-ion Download PDF

Info

Publication number
WO2011069331A1
WO2011069331A1 PCT/CN2010/001974 CN2010001974W WO2011069331A1 WO 2011069331 A1 WO2011069331 A1 WO 2011069331A1 CN 2010001974 W CN2010001974 W CN 2010001974W WO 2011069331 A1 WO2011069331 A1 WO 2011069331A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium ion
ion battery
battery according
lithium
inorganic
Prior art date
Application number
PCT/CN2010/001974
Other languages
English (en)
Chinese (zh)
Inventor
李翔
唐杰
孙庆津
徐晟�
罗建海
Original Assignee
微宏动力系统（湖州）有限公司
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 微宏动力系统（湖州）有限公司 filed Critical 微宏动力系统（湖州）有限公司
Priority to US13/514,973 priority Critical patent/US9281540B2/en
Publication of WO2011069331A1 publication Critical patent/WO2011069331A1/fr

Links

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
    • H01M10/052—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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • 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
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/426—Fluorocarbon polymers
    • 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
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • 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
    • H01M2300/0068—Solid electrolytes inorganic
    • 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
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

Definitions

  • the present invention relates to the field of lithium ion batteries and similar storage technologies, and more particularly to a lithium ion battery comprising an ion selective conduction layer.
  • Lithium-ion batteries have the advantages of high weight and volume energy density, long cycle life, a certain degree of safety and reliability, and the ability to perform rapid charge and discharge. In recent years, they have become a hot spot in the research and development of new energy storage technologies. High energy and high power applications are popular.
  • a typical lithium ion secondary battery is composed of a positive and negative electrode material, an electrolyte, a separator, and a battery casing packaging material.
  • a polymer lithium ion battery refers to a lithium ion battery in which an electrolyte uses a solid polymer electrolyte (SPE).
  • the battery is compounded by a positive current collector, a positive electrode film, a solid polymer electrolyte membrane, a negative electrode membrane, and a negative current collector, and the outer package is an aluminum-plastic composite film, and the edges thereof are heat-sealed to obtain a polymer lithium ion battery.
  • Existing solid polymer electrolyte membrane is doped with a proportion of inorganic particles such as Si0 2, A1 2 0 3 and LiCF 3 S0 3 directly as a polymer film such as an electrolyte, typically a polymer with a polyethylene oxide Alkene PE0, etc., such electrolytes generally have a thickness of more than 100 Mm, and lithium ions in the electrolyte can move in the molecular chain.
  • the copper ions oxidized as a current collector metal such as copper foil can pass through the solid polymer electrolyte membrane relatively smoothly. Once the battery is over-discharged, the copper foil is easily oxidized, so that a large amount of copper ions can be smoothly performed.
  • Chinese Patent C '2922234 discloses an over-discharge protection circuit for a power lithium-ion battery, comprising a pair of input and output ports and a battery unit, a port at the pair of input and output ports and an electrode of the battery unit Interconnecting a discharge control switch, wherein the battery unit is formed by connecting a plurality of lithium ion rechargeable batteries in series; and further comprising an overdischarge voltage detecting unit that compares a voltage of the battery with a set voltage and outputs a comparison result, according to which Output of discharge voltage detecting unit The signal controls an overdischarge logic control unit that turns on/off the discharge control switch.
  • the overdischarge protection circuit can automatically disconnect the circuit and stop the discharge, so that any one of the batteries will not Damaged by over-discharge, ensuring safe discharge of the battery unit.
  • Cia patent Q 101404406 discloses a lithium battery protection circuit: the protection circuit is composed of an overcharge control tube, an overdischarge control tube and a protection IC, and the overcharge control tube and the overdischarge control tube are monitored by the protection IC and controlled.
  • the protection IC is a CMOS integrated circuit block, which includes an overcharge protection circuit, an overdischarge protection circuit and an overcurrent protection circuit.
  • the protection IC is provided between the output negative V- and the gate of the MOS transistor connected to the output negative V-.
  • Chinese patent CN101159375 discloses a lithium battery power supply control protection circuit and a control and protection method. The method described above controls the battery power supply to prevent overdischarge by detecting the battery voltage, and can completely shut down the battery through software.
  • the purpose of preventing excessive discharge of the lithium ion battery is achieved by an external circuit design, and the damage to the battery caused by the problem of excessive discharge of the lithium ion battery cannot be eliminated in essence or from the inside of the battery.
  • High-capacity battery packs or battery pack systems often consist of thousands or even tens of thousands of single cells. This external circuit protection design is difficult to protect single cells, and the reliability of the circuit is difficult to guarantee, and the management cost. Higher.
  • the technical problem to be solved by the present invention is that the prior art cannot substantially eliminate the excessive discharge of the lithium ion battery inside the battery to cause damage to the battery itself.
  • the metal used for the anode current collector in most cases, copper metal
  • the discharge is negative, the negative electrode is oxidized and loses electrons.
  • the overdischarge occurs, the lithium ion of the negative electrode will migrate to the positive electrode according to equation (1).
  • the copper metal of the current collector will follow the equation ( The form of 2) is oxidized, and copper ions generated by oxidation of copper will migrate toward the positive electrode and precipitate on the surface of the positive electrode material or on the separator.
  • the technical solution provided by the present invention is: adding a conductive layer having preferential selective conduction to lithium ions between the positive electrode and the negative electrode of the lithium ion battery, and the selective conductive layer has a comparative layer A good lithium ion pass rate, while at the same time, the battery is over-discharged to cause a metal ion generated by the current collector of the negative electrode to have a blocking effect.
  • the lithium ion battery claimed in the present invention comprises a positive electrode, a negative electrode and an electrolyte system, and an ion selective conductive layer is further included between the positive electrode and the negative electrode, and the ion selective conductive layer is composed of a high molecular polymer and an inorganic having lithium ion conductivity.
  • the electrolyte system may be an organic electrolyte system.
  • the organic electrolyte is at least one of LiPF 6 , LiAsFa, LiC10 4 or LiBF 4 as an electrolyte, and at least one of EC, PC, EPC, BC; DME, DMC, EMC, DEC or DMF is An organic solution prepared by solvent.
  • the active material on the positive electrode includes at least one of commonly used, commercially available LiCoO 2 , LiNiO 2 Li n 2 0 4 > 6?0 4 or other composite oxide.
  • the negative electrode includes a current collector made of any one of copper, nickel, aluminum, and stainless steel alloy.
  • the active material on the negative electrode includes any of the existing negative electrode materials, especially carbonaceous materials or materials containing lithium titanate.
  • the area of the ion selective conductive layer is preferably not less than the area of the negative electrode, such that the ion selective conductive layer can completely isolate the negative electrode from the positive electrode and completely prevent conduction of electrons between the positive electrode and the negative electrode inside the battery.
  • the commonly used separators in commercial lithium-ion batteries are mostly porous membranes, and there are lithium ions directly penetrating both sides of the membrane. Physical through hole.
  • the ion selective conductive layer in the lithium ion battery claimed in the present invention is dense, and lithium ions cannot directly penetrate the conductive layer.
  • the ion selective conductive layer described in the present invention has the function that lithium ions can exchange lithium ions with an inorganic lithium salt having lithium ion conductivity, thereby realizing lithium ion conduction, thereby effectively preventing generation of a current current collector after being oxidized. The passage of other metal ions.
  • the inorganic lithium salt having lithium ion conductivity include Li 0 7, LiB0 2, Li 4 Si0 4, Li 2 Se0 4, Li 2 Zr0 3, Li, Li 2 Ti0 3, Li 2 Te0 3, Li 2 Ta0 3, LiA10 2, Li 3 As0 4, a -LiAlSiA in any one of, or a mixture of any two or wherein preferably Li 2 B 4 0 7, Li 2 Zr0 3 , Li 2 Ti0 3 , Li 4 SiQ ⁇ , LiA10 2 , 1 ⁇ 80 2 or . - ⁇ At least one of eight 18 0 6 .
  • M in the inorganic lithium salt Li 0 x according to the present invention includes the element P, wherein M may include at least one of B, Si, C, Al, Ti or Zr in addition to P.
  • the inorganic lithium salt having lithium ion conductivity particularly preferably includes Li 3 P0 4 .
  • the ion selective conductive layer may be a dense film formed by a high molecular polymer and an inorganic lithium salt having lithium ion conductivity, and there is no simultaneous penetration between the two sides of the film. Physical through hole.
  • the inorganic lithium salt is uniformly dispersed in the high molecular polymer.
  • the high molecular polymer includes PAN' (polyacrylonitrile), P MA (polymethyl methacrylate), PVDF (polyvinylidene fluoride) or PVC (polyvinyl chloride), PVDF-HFP (polyimide) At least one of vinyl fluoride-hexafluoropropylene), PVDF-CTFE (polyvinylidene fluoride-trichloroethylene), PS (polysulfone) or PES (polyethersulfone).
  • Copolymers or homopolymers comprising PVDF are preferred; and PVDF copolymers include PVDF HFP, PVDF The homopolymer consists of PVDF.
  • This dense film can be attached to the porous film inside the existing battery, and the dense film of the present invention is bonded to at least one side of the porous film.
  • This dense film can also be used independently, such as directly as a battery separator or attached to the positive and negative surfaces of the battery.
  • the ion selective conductive layer may further be a thin layer composed of an inorganic lithium salt covering at least one surface of the positive electrode and the negative electrode.
  • the lithium ion battery claimed in the present invention has the ability to prevent internal short circuit of the battery and to increase the cycle life of the battery when it is over-discharged or subjected to abnormal reverse charging.
  • the ion selective conductive layer contained therein has a good lithium ion conducting function, and has a barrier effect on the metal ions generated after the negative current collector is oxidized.
  • the ion selective conductive layer is between the negative electrode and the electrolyte, for example, covering the surface of the negative electrode material, the lithium "dendritic" phenomenon caused by charging or overcharging of the lithium ion battery can be effectively prevented, thereby preventing the battery Internal short circuit.
  • Fig. 1 is a flow chart showing a process for preparing an ion-selective conductive film comprising Li 3 P0 4 of the present invention.
  • Example 2 is a SEM photograph of a porous structural surface of an ion-selective conductive film containing 1 ⁇ 3 ?0 4 prepared in Example 1 of the present invention.
  • 3 is a SEM photograph of a dense surface of an ion-selective conductive film containing 1 ⁇ 4 4 prepared in Example 1 of the present invention.
  • Example 4 is a SEM photograph of a cross section of an ion-selective conductive film containing 1 ⁇ 3 ?0 4 prepared in Example 1 of the present invention.
  • Fig. 5 is an XRD chart showing the surface of a positive electrode material after disassembly of a battery made of a Celgard 2320 separator in Example 4 of the present invention.
  • Fig. 6 is an XRD chart showing the surface of a positive electrode material after disassembly of a lithium ion battery manufactured in Example 3 of the present invention.
  • Fig. 7 is an XRD chart showing the surface of a lithium ion battery film produced in Example 3 of the present invention.
  • Figure 8 is an AC impedance map of different separators in Example 2 of the present invention.
  • the pulverization method may include ball milling, sanding, airflow pulverizing, ultrafine pulverizing grinding, etc.;
  • the obtained slurry system is cast into a film by a casting machine, and the thickness is 5 ⁇ 50 after drying.
  • the film forming process is a mature casting process, and the apparent structure of the film is as follows:
  • the other side is a smoother and dense structure.
  • the non-smooth side may make the film itself have good wettability with the electrolyte, so that the film resistance can be effectively reduced.
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene
  • the obtained slurry was filtered and defoamed, and cast into a film on a carrier film having a smooth surface using a film casting machine, and dried to obtain a dense film having a film thickness of 20 ⁇ m.
  • the side of the dense film and the carrier film is smooth and dense, and the other side is a matte structure.
  • the surface of the separator was analyzed by scanning electron microscopy (SEM), as shown in Fig. 2. It can be seen from the figure that the surface is not smooth; as shown in Fig. 3, the surface of the separator is etched. It is relatively smooth and dense;
  • Figure 4 shows the cross-sectional structure of the Li 3 P0 4 ion selective conductive film.
  • Test method The membrane was clamped between standard gaskets with a 1.0 mm square hole through a gas permeability tester with a small hole in the center of the gasket to allow gas to flow through, under a steady pressure, a certain measurement The volume of gas (100 cc) required to flow through a sample of a specific area. Using the ion selective conductive membrane containing Li 3 P0 4 prepared above as a test, 100 cc of gas still failed to flow for 30 minutes. The same test was carried out using a commercial Celgard 2320 diaphragm, and 100 cc of gas was completely flowed in 350-450 seconds.
  • the ion selective conductive film containing 1 ⁇ 4 4 prepared in Example 1 and the Celgard 2320 separator (both thicknesses of 20 Mm) were used in the electrolyte (LiPF 6 /EC-DEC, the volume ratio of EC to DEC was 1 : 1 ) Fully soaked, the diaphragm was sandwiched between two blocking electrodes made of two stainless steel sheets in an Ar atmosphere glove box, and an AC impedance measurement was performed using an electrochemical workstation at room temperature. The measured data is shown in Fig. 8.
  • the solid line represents the AC impedance curve including the Li 3 P0 ion selective conductive film
  • the broken line represents the AC impedance curve of the Celgard 2320 diaphragm, from which it can be seen that:
  • Example 1 The dense film has a lower pure resistance than the Celgard 2320 separator, and the lithium ion conductivity is higher.
  • Preparation of positive electrode According to the ratio, the positive electrode active material lithium iron phosphate (LiFeP0, 87 W t%, conductive carbon black 5 W t%, binder polyvinylidene fluoride PVDF 8 wt%), evenly dispersed in N-A
  • the positive electrode active material lithium iron phosphate (LiFeP0, 87 W t%, conductive carbon black 5 W t%, binder polyvinylidene fluoride PVDF 8 wt%), evenly dispersed in N-A
  • MP bis-2-pyrrolidone
  • the negative active material (charcoal powder 92 wt%, conductive carbon black 2 wt%, binder polyfluoride
  • the olefin PVDF is 6 wt%) uniformly dispersed in the X-methyl-2-pyrrolidine I (XP) solution to prepare a mixed slurry of the negative electrode, and the slurry is coated on the negative current collector copper foil. After the dry roll was pressed, a negative electrode tab was obtained.
  • Example 3 A lithium ion battery fabricated in Example 3 and a lithium ion battery fabricated using a Celgard 2320 separator were subjected to a comparative test:
  • the two sets of batteries subjected to reverse polarity charging were disassembled separately, and the surface of the positive electrode material of the battery made of Celgard 2320 diaphragm was subjected to XRD test, and the XRD pattern showed clear peaks of copper metal XRD (as shown in Fig. 5).
  • the battery prepared in Example 3 was free from metallic copper on the surface of the positive electrode material of the disassembled battery, and no peak of copper metal appeared on the surface of the positive electrode material by XRD (Fig. 6).
  • the XRD test on the diaphragm also showed no peaks of copper metal (as shown in Figure 7), and the same fabricated battery could continue to charge and discharge after the reverse polarity charging.
  • Example 3 A lithium ion battery fabricated in Example 3 and a lithium ion battery fabricated using a Celgard 2320 separator were subjected to a comparative test:
  • the discharge voltage of the two sets of lithium-ion batteries was reduced from the usual 2. 5 V voltage to 1. 0 V and 0.1 V, and the battery cycle performance test was performed with a discharge current of 0.5 C.
  • the lithium ion battery fabricated in Example 3 can still work normally after 30 overdischarge cycles, and the lithium ion battery fabricated using the Celgard 2320 separator exhibits significant capacity degradation after 10 times of the same overdischarge cycle. Basically, normal charging and discharging cannot be performed.
  • PVDF-HFP polyvinylidene fluoride-hexafluoropropylene
  • the obtained slurry was filtered and defoamed, and a film casting machine was used to cast a film on the surface of a positive electrode sheet of a lithium ion battery, and after drying, a dense positive electrode electrode piece was obtained, and the thickness was 20 Mm. After drying and rolling, it can be made into a lithium ion battery with a negative electrode of a lithium ion battery and an electrolyte, and no additional separator is needed.
  • the obtained slurry was filtered and defoamed, and a film casting machine was used to cast a film on the surface of a lithium ion battery negative electrode sheet which was formed into a film, and dried to obtain a dense film having a thickness of 20 ⁇ . After drying and rolling, it can be made into a lithium ion battery with a positive electrode of a lithium ion battery and an electrolyte, and no additional separator is needed.
  • 5 g of polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) was dissolved in a mixed solvent of 149.2 g of acetone and 200 g of 1-methyl-2-pyrrolidinium (NMP), and stirred until the mixture was dispersed.
  • the vinyl fluoride was completely dissolved, and then 78. 6 g of lithium phosphate powder was added, and the mixture was ground and dispersed until a uniform slurry was obtained.
  • the obtained slurry was filtered and defoamed, and a film casting machine was used to strictly control the distance between the cutter head and the carrier tape, and the film was cast on a smooth carrier film to provide a film thickness of 5 Wn.
  • the above-mentioned film having a thickness of 5 Mm is subjected to hot press lamination with a conventional physical through-hole film widely used in a lithium ion battery, and the pressing temperature is controlled to 120 V, and the pressure is 0.35 kg/cm 2 , which is obtained by including 1 ⁇ 0 4 .
  • the inorganic lithium salt having lithium ion conductivity in the ion selective conductive layer in the above embodiment is not limited to Li 3 P0 4 , and may be Li 3 P0 4 doped with B, Si, C. Al, Ti. Or a compound of any one or two of Zr.
  • the inorganic lithium salt having lithium ion conductivity may also be Li 2 B 4 0 7 , Li 2 ZrO 3 , Li 2 W0., Li 2 TiO 3 , Li 2 TeO Lija 0 3 , Li 2 Se0 4 , Li 4 SiO.
  • LiA10 2 , LiF, LiB0 2 , Li 3 As0 4 or a - LiAlSi 2 0 6 because they contain lithium ions as compared with Li 3 P0 4 and due to their crystal structure characteristics and The crystal defects after doping enable lithium ion exchange and conduction functions.
  • the high molecular polymer includes at least one of PAN or PVC in addition to PVDF.
  • PVDF-HFP is preferred because PVDF-HFP has good chemical stability in the electrolyte and PVDF as a binder in the lithium ion battery electrode, so the PVDF polymer material has a very high capacity in a lithium ion battery. Good chemical compatibility.

Landscapes

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

Abstract

Cette invention concerne une batterie lithium-ion, comprenant une électrode positive, une électrode négative, un corps électrolytique et une couche conductrice à sélectivité ionique disposée entre l'électrode positive et l'électrode négative. Ladite couche conductrice à sélectivité ionique consiste en un polymère lourd et un sel de lithium inorganique, ou un sel de lithium inorganique à conductivité ionique. Ledit sel de lithium inorganique comprend un LimMnOx, où la valeur des indices m, n assure l'électroneutralité du LimMnOx, M étant au moins un élément choisi dans le groupe comprenant B, P, Si, Se, Zr, W, Ti, Te, Ta, Al ou As. La batterie lithium-ion comprend une couche conductrice à préférence aux ions de lithium disposée entre l'électrode positive et l'électrode négative, la couche conductrice sélective assurant une meilleure mobilité des ions de lithium tout en ayant un effet obstructif vis-à-vis des ions métalliques générés par l'oxygénation du collecteur de courant négatif métallique due à une surdécharge de la batterie.
PCT/CN2010/001974 2009-12-09 2010-12-06 Batterie lithium-ion WO2011069331A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/514,973 US9281540B2 (en) 2009-12-09 2010-12-06 Lithium-ion battery comprising an ion-selective conducting layer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200910155309.7 2009-12-09
CN200910155309.7A CN102097647B (zh) 2009-12-09 2009-12-09 锂离子电池

Publications (1)

Publication Number Publication Date
WO2011069331A1 true WO2011069331A1 (fr) 2011-06-16

Family

ID=44130582

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2010/001974 WO2011069331A1 (fr) 2009-12-09 2010-12-06 Batterie lithium-ion

Country Status (3)

Country Link
US (1) US9281540B2 (fr)
CN (1) CN102097647B (fr)
WO (1) WO2011069331A1 (fr)

Families Citing this family (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103085677B (zh) * 2011-11-08 2015-09-02 微宏动力系统（湖州）有限公司 车用电能动力系统
CN102832367B (zh) * 2012-08-31 2014-12-31 浙江大东南包装股份有限公司 一种锂离子二次电池隔膜及其制备方法
US9236161B2 (en) * 2012-09-06 2016-01-12 E I Du Pont De Nemours And Company Conductive paste composition and semiconductor devices made therewith
CN103178293B (zh) * 2013-02-07 2015-01-28 天津大学 圆柱形单体400Ah锂离子电池及其制备方法
WO2014121528A1 (fr) 2013-02-07 2014-08-14 天津大学 Pile cylindrique au lithium-ion au monomère 400 ah et son procédé de préparation
CN104051693B (zh) * 2014-06-16 2016-06-01 中国东方电气集团有限公司 一种锂离子电池用多金属氧酸锂盐陶瓷隔膜
TWI528619B (zh) 2014-07-16 2016-04-01 輝能科技股份有限公司 金屬鋰極板
CN106716549B (zh) * 2014-11-10 2020-03-24 株式会社村田制作所 玻璃陶瓷、锂离子导体、电池、电子装置及电极的制造方法
JP2018525533A (ja) * 2015-05-30 2018-09-06 クリーン リチウム コーポレーション 高純度リチウム、関連する生成物、及び方法
CN105140449A (zh) * 2015-08-14 2015-12-09 中国人民解放军63971部队 一种保护锂硫电池负极的方法
CN105552352A (zh) * 2016-02-03 2016-05-04 山东康洋电源有限公司 一种新能源汽车专用动力型锂离子电池
CN106876633A (zh) * 2017-02-22 2017-06-20 北京卫蓝新能源科技有限公司 一种复合隔膜、锂电池及其制备方法
KR102268176B1 (ko) * 2017-08-28 2021-06-22 주식회사 엘지에너지솔루션 리튬 이차전지
JP6889125B2 (ja) 2018-03-16 2021-06-18 株式会社東芝 セパレータ、電極群、二次電池、電池パック、車両、及び定置用電源
CN110661033B (zh) * 2018-06-28 2021-06-22 宁德时代新能源科技股份有限公司 离子交换材料及其制备方法、电解质薄膜、二次电池
WO2020054099A1 (fr) 2018-09-13 2020-03-19 Kabushiki Kaisha Toshiba Batterie secondaire, bloc-batterie, véhicule et alimentation électrique fixe
CN109817865B (zh) * 2018-12-19 2022-10-21 航天科工(长沙)新材料研究院有限公司 一种复合隔膜及其制备方法
CN111490228B (zh) * 2019-01-29 2021-07-27 广州汽车集团股份有限公司 一种锂电池用电极及其制备方法与含有该电极的锂电池
KR102195187B1 (ko) * 2019-02-18 2020-12-28 주식회사 에스엠랩 양극활물질, 이의 제조방법 및 이를 포함하는 양극을 포함한 리튬이차전지
US11811088B2 (en) 2019-09-19 2023-11-07 Kabushiki Kaisha Toshiba Separator, electrode group, secondary battery, battery pack, vehicle, and stationary power supply
CN111392718B (zh) * 2019-12-23 2023-03-28 余姚市鑫和电池材料有限公司 一种退役锂电池负极材料再利用方法
CN112202213A (zh) * 2019-12-31 2021-01-08 浙江华友循环科技有限公司 一种锂离子电池模组物理放电设备及其物理放电方法
CN111653712B (zh) * 2020-05-21 2021-09-28 上海恩捷新材料科技有限公司 一种电化学装置隔离膜及其制备方法
CN111725559B (zh) * 2020-07-06 2021-06-22 电子科技大学 固态电解质及其制备方法和锂二次固态电池
CN113093031B (zh) * 2021-03-19 2024-01-19 北京工业大学 一种基于电压逆推检测锂离子电池正极材料过放电程度的方法
CN114006130A (zh) * 2021-09-27 2022-02-01 河北金力新能源科技股份有限公司 一种高耐热补锂隔膜浆料、隔膜和锂电池
CN114583172B (zh) * 2022-03-07 2023-12-15 中南大学 一种人造sei材料、sei膜及其制备和在金属锂电池中的应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1258939A2 (fr) * 2001-05-15 2002-11-20 Hitachi, Ltd. Batterie secondaire au lithium
CN1490891A (zh) * 2002-07-10 2004-04-21 索尼公司 电池
CN101010827A (zh) * 2004-12-07 2007-08-01 株式会社Lg化学 含氧阴离子的非水系电解液和使用该电解液的锂二次电池
CN101188312A (zh) * 2007-10-12 2008-05-28 广州市鹏辉电池有限公司 非水溶剂电解液添加剂及其电池

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6413284B1 (en) * 1999-11-01 2002-07-02 Polyplus Battery Company Encapsulated lithium alloy electrodes having barrier layers
KR100440930B1 (ko) * 2001-11-24 2004-07-21 삼성에스디아이 주식회사 세퍼레이터의 제조방법 및 이를 채용한 리튬2차 전지의제조방법
KR100590376B1 (ko) 2003-03-20 2006-06-19 마쯔시다덴기산교 가부시키가이샤 집합전지
US7468224B2 (en) * 2004-03-16 2008-12-23 Toyota Motor Engineering & Manufacturing North America, Inc. Battery having improved positive electrode and method of manufacturing the same
US20060078790A1 (en) * 2004-10-05 2006-04-13 Polyplus Battery Company Solid electrolytes based on lithium hafnium phosphate for active metal anode protection
CN2922234Y (zh) 2006-06-08 2007-07-11 潍坊光华电池有限公司 动力锂离子电池的过放电保护电路
CN100539349C (zh) 2007-09-21 2009-09-09 江苏金智科技股份有限公司 锂电池供电控制保护电路及控制保护方法
CN101404406B (zh) 2008-07-15 2011-08-03 无锡华润上华科技有限公司 一种锂电池保护电路

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1258939A2 (fr) * 2001-05-15 2002-11-20 Hitachi, Ltd. Batterie secondaire au lithium
CN1490891A (zh) * 2002-07-10 2004-04-21 索尼公司 电池
CN101010827A (zh) * 2004-12-07 2007-08-01 株式会社Lg化学 含氧阴离子的非水系电解液和使用该电解液的锂二次电池
CN101188312A (zh) * 2007-10-12 2008-05-28 广州市鹏辉电池有限公司 非水溶剂电解液添加剂及其电池

Also Published As

Publication number Publication date
US20120251891A1 (en) 2012-10-04
CN102097647B (zh) 2014-03-26
CN102097647A (zh) 2011-06-15
US9281540B2 (en) 2016-03-08

Similar Documents

Publication Publication Date Title
WO2011069331A1 (fr) Batterie lithium-ion
CN101796668B (zh) 电池用隔膜及非水电解液电池
US9401505B2 (en) Separator including coating layer of inorganic and organic mixture, and battery including the same
KR100802870B1 (ko) 권회형 비수계 이차전지 및 이것에 이용하는 전극판
JP5328034B2 (ja) 電気化学素子用セパレータ、電気化学素子およびその製造方法
CN101617433B (zh) 电化学元件及其制造方法
US8343388B2 (en) Electrode having porous active coating layer, manufacturing method thereof and electrochemical device containing the same
KR102284480B1 (ko) 유무기 복합 전해질, 이를 포함하는 전극-전해질 접합체 및 리튬이차전지, 및 상기 전극-전해질 접합체의 제조방법
EP2634840B1 (fr) Séparateur comprenant une couche de revêtement à densité contrôlée et batterie comprenant celui-ci
JP5241314B2 (ja) ラミネート形非水二次電池
KR101897391B1 (ko) 적층체, 이차 전지, 전지 팩 및 차량
US20220223899A1 (en) Partition for electrochemical apparatus, electrochemical apparatus, and electronic apparatus
JP4367951B2 (ja) 非水二次電池
US20060019151A1 (en) Non-aqueous electrolyte battery
US20070037049A1 (en) Auxiliary power unit
WO2005098997A1 (fr) Batterie secondaire à électrolytes non aqueux
US20240047827A1 (en) Battery, Electronic Device, and Mobile Apparatus
JP5464766B2 (ja) 電池用セパレータおよび非水電解液電池
EP4318777A1 (fr) Séparateur, et dispositif électrochimique et dispositif électronique le comprenant
WO2024077822A1 (fr) Séparateur et son procédé de préparation, batterie rechargeable, et dispositif électrique
CN114982035A (zh) 电池组、电池包、电学装置以及电池组的制造方法及制造设备
CN103299452A (zh) 蓄电设备用分隔物及蓄电设备
US20220223968A1 (en) Partition plate for use in electrochemical device, electrochemical device, and electronic device
CN116686153A (zh) 电极极片及包含其的二次电池
WO2020059874A1 (fr) Batterie secondaire

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10835368

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 13514973

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10835368

Country of ref document: EP

Kind code of ref document: A1