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WO2015118676A1 - Matériau pour batteries au lithium - Google Patents

Matériau pour batteries au lithium Download PDF

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Publication number
WO2015118676A1
WO2015118676A1 PCT/JP2014/052991 JP2014052991W WO2015118676A1 WO 2015118676 A1 WO2015118676 A1 WO 2015118676A1 JP 2014052991 W JP2014052991 W JP 2014052991W WO 2015118676 A1 WO2015118676 A1 WO 2015118676A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
negative electrode
lithium ion
ion secondary
secondary 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.)
Ceased
Application number
PCT/JP2014/052991
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English (en)
Japanese (ja)
Inventor
紀雄 岩安
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.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
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Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Priority to PCT/JP2014/052991 priority Critical patent/WO2015118676A1/fr
Publication of WO2015118676A1 publication Critical patent/WO2015118676A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—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
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/137—Electrodes based on electro-active polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active 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

Definitions

  • the present invention relates to a material for a Li battery.
  • Patent Document 1 discloses a technique for coating a negative electrode active material with a polyamideimide resin.
  • an object is to provide a novel coating material for a negative electrode active material that achieves both a reduction in irreversible capacity and a reduction in battery resistance.
  • a negative electrode coating material for a lithium ion secondary battery represented by Formula (1) A negative electrode coating material for a lithium ion secondary battery represented by Formula (1).
  • R 3 , R 4 and R 5 in the formula (1) are each a hydrocarbon group having 1 to 10 carbon atoms or H.
  • R 1 and R 2 have at least one electron-withdrawing functional group.
  • n is the number of repeating structural units.
  • Examples of the negative electrode covering material for a lithium ion secondary battery represented by Formula (1) include Formula (5), Formula (6), Formula (7), and Formula (8).
  • N in Formula (5), Formula (6), Formula (7), and Formula (8) is the number of repeating structural units.
  • a negative electrode having a small irreversible capacity and a low resistance can be provided.
  • a lithium ion secondary battery having high capacity and excellent output characteristics can be provided.
  • FIG. 1 is a diagram schematically showing the internal structure of a battery according to an embodiment of the present invention.
  • a battery 1 according to an embodiment of the present invention shown in FIG. 1 includes a positive electrode 10, a separator 11, a negative electrode 12, a battery container (that is, a battery can) 13, a positive electrode current collecting tab 14, a negative electrode current collecting tab 15, an inner lid 16, It comprises an internal pressure release valve 17, a gasket 18, a positive temperature coefficient (PTC) resistance element 19, a battery lid 20, and an axis 21.
  • the battery lid 20 is an integrated part composed of the inner lid 16, the internal pressure release valve 17, the gasket 18, and the PTC resistance element 19.
  • a positive electrode 10, a separator 11, and a negative electrode 12 are wound around the shaft center 21.
  • the separator 11 is inserted between the positive electrode 10 and the negative electrode 12 to produce an electrode group wound around the axis 21.
  • the electrode group has various shapes such as a laminate of strip electrodes, or a positive electrode 10 and a negative electrode 12 wound in an arbitrary shape such as a flat shape. Can do.
  • the shape of the battery case 13 may be selected from shapes such as a cylindrical shape, a flat oval shape, a flat oval shape, and a square shape according to the shape of the electrode group.
  • the material of the battery container 13 is selected from materials that are corrosion resistant to non-aqueous electrolytes, such as aluminum, stainless steel, and nickel-plated steel. Further, when the battery container 13 is electrically connected to the positive electrode 10 or the negative electrode 12, the material is not deteriorated due to corrosion of the battery container 13 or alloying with lithium ions in the portion in contact with the nonaqueous electrolyte. Thus, the material of the battery container 13 is selected.
  • the electrode group is housed in the battery container 13, the negative electrode current collecting tab 15 is connected to the inner wall of the battery container 13, and the positive electrode current collecting tab 14 is connected to the bottom surface of the battery lid 20.
  • the electrolyte is injected into the battery container interior 13 before the battery is sealed.
  • a method for injecting the electrolyte there are a method of adding directly to the electrode group in a state where the battery cover 20 is released, or a method of adding from an injection port installed in the battery cover 20.
  • the battery lid 20 is brought into close contact with the battery container 13 to seal the entire battery. If there is an electrolyte inlet, seal it as well.
  • a method for sealing the battery there are known techniques such as welding and caulking.
  • the lithium ion battery according to an embodiment of the present invention can be manufactured, for example, by disposing a negative electrode and a positive electrode as described below with a separator interposed therebetween and injecting an electrolyte.
  • the structure of the lithium ion battery according to an embodiment of the present invention is not particularly limited.
  • the positive electrode and the negative electrode and the separator separating them are wound into a wound electrode group, or the positive electrode, the negative electrode, and the separator are combined.
  • a stacked electrode group can be formed by stacking.
  • the positive electrode 10 includes a positive electrode active material, a conductive agent, a binder, and a current collector.
  • the positive electrode active material include LiCoO 2 , LiNiO 2 , and LiMn 2 O 4 .
  • the particle size of the positive electrode active material is usually specified so as to be equal to or less than the thickness of the mixture layer formed of the positive electrode active material, the conductive agent, and the binder.
  • the coarse particles can be removed in advance by sieving classification or wind classification to produce particles having a thickness of the mixture layer thickness or less. preferable.
  • the positive electrode active material is generally oxide-based and has high electric resistance
  • a conductive agent made of carbon powder for supplementing electric conductivity is used. Since both the positive electrode active material and the conductive agent are usually powders, a binder can be mixed with the powders, and the powders can be bonded together and simultaneously bonded to the current collector.
  • an aluminum foil having a thickness of 10 to 100 ⁇ m, an aluminum perforated foil having a thickness of 10 to 100 ⁇ m and a pore diameter of 0.1 to 10 mm, an expanded metal, a foam metal plate, or the like is used.
  • materials such as stainless steel and titanium are also applicable.
  • any current collector can be used without being limited by the material, shape, manufacturing method and the like.
  • a positive electrode slurry in which a positive electrode active material, a conductive agent, a binder, and an organic solvent are mixed is attached to a current collector by a doctor blade method, a dipping method, or a spray method, and then the organic solvent is dried and applied by a roll press.
  • the positive electrode 10 can be produced by pressure forming.
  • a plurality of mixture layers can be laminated on the current collector by performing a plurality of times from application to drying.
  • the negative electrode in the present invention comprises a negative electrode active material, a binder, and a current collector.
  • the negative electrode active material an easily graphitized material obtained from natural graphite, petroleum coke, coal pitch coke, etc.
  • the coating material preferably has ionicity to the extent that lithium ions are captured and dissociated.
  • the lithium ion capturing power of the covering material is too strong, the lithium ion conductivity is increased and the output as a battery is inferior. Therefore, it is preferable that the bonding force between the coating material and the lithium ions be adjusted strictly.
  • Examples of the functional group containing F include F, CFH 2 , CF 2 H, and CF 3 . From the viewpoint of synthesis, F and CF 3 are preferably used.
  • the other functional group when there is one electron-withdrawing group, the other functional group is hydrogen or a hydrocarbon group.
  • R1 and R2 are located adjacent to the sulfo group.
  • the electron-withdrawing functional group is located adjacent to the sulfo group, the electron density of the sulfo group decreases, and as a result, the degree of dissociation of Li ions increases, and the resistance of the battery can be reduced.
  • a coating material a copolymer obtained by copolymerizing a first monomer corresponding to a polymer having a structure of formula (1) (for example, formula (4)) with another second monomer. By copolymerization, a higher irreversible capacity reduction effect is exhibited.
  • a second monomer having the structure of formula (9) to formula (13) is preferably used as the monomer to be copolymerized.
  • X of the monomer is an alkali metal or H, and the alkali metal is preferably used from the viewpoint of electrochemical stability.
  • the initiator content in the present invention is 0.1 wt% to 20 wt%, preferably 0.3 wt% or more and 5 wt% with respect to the polymerizable compound.
  • the polymer structure may be a linear structure, a branched structure, a crosslinked structure, or a dendrimer structure. From the viewpoint of workability at the time of coating, a linear polymer is preferably used.
  • the polymerization mode when monomers are copolymerized is not particularly limited as long as a polymer can be formed, and examples thereof include random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization.
  • the number average molecular weight of the polymer used as the negative electrode coating material of the present invention is 1,000 or more and 5,000,000 or less. Preferably it is 1000 or more and 1,000,000 or less. By adjusting the number average molecular weight, aggregation of the negative electrode active material, which tends to occur when coating, can be suppressed.
  • the copolymer composition ratio of the first monomer corresponding to the polymer having the structure of the formula (1) and the second monomer containing the structures of the formulas (9) to (13) is the effect of the present invention. It is important in getting.
  • Formula (9), Formula (10), Formula (11), Formula (12), and Formula (13) can each be homopolymerized, and this polymer and the polymer of Formula (1) are mixed to form a negative electrode
  • the active material can also be coated.
  • non-aqueous solvents examples include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, fluoroethylene carbonate, ⁇ -butyrolactone, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, 1,2- Dimethoxyethane, 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, methyl propionate, ethyl propionate, phosphate triester, trimethoxymethane, dioxolane, diethyl ether, sulfolane, 3- Non-methyl-2-oxazolidinone, tetrahydrofuran, 1,2-diethoxyethane, chloroethylene carbonate, chloropropylene carbonate, etc.
  • solvent There is a solvent.
  • Other solvents may be used as long as they do not decompose on the positive electrode 10 or the negative electrode
  • tetrahydrofuran as a monomer and reaction solvent was added to a reaction vessel. Furthermore, AIBN was added to the solution as a polymerization initiator. The concentration of the polymerization initiator was added so as to be 4 wt% with respect to the total amount of monomers. Thereafter, the polymer solutions (8) and (6) were synthesized by heating the reaction solution at 60 ° C. for 3 hours.
  • the negative electrode active material is added to the solution and stirred. After stirring for 20 minutes, the negative electrode active material in the form of a slurry is taken out and placed in a dryer heated to 100 ° C. to remove water. Then, after drying with a vacuum dryer heated to 120 ° C., it was sieved to obtain a coated negative electrode active material. The coating polymer was 0.5 wt% with respect to the negative electrode active material. In addition, graphite was used as the negative electrode active material. ⁇ Method for producing negative electrode> Polyvinylidene fluoride was mixed with graphite at a weight ratio of 95: 5, and charged into N-methyl-2-pyrrolidone to prepare a slurry solution.
  • the irreversible capacity was 33 mAhg- 1 .
  • a small battery was produced, and DC resistance was measured.
  • the DC resistance was 9.9 ⁇ .
  • a monomer was synthesized by copolymerizing the monomer (x) of the formula (14) and the monomer (y) of the formula (11). The copolymer composition ratio (x / (x + y)) was 0.75.
  • a negative electrode single electrode was prepared and the irreversible capacity was measured. The irreversible capacity was 28 mAhg- 1 .
  • a small battery was produced, and DC resistance was measured. The DC resistance was 10.9 ⁇ .
  • Example 1 Evaluation was performed in the same manner as in Example 1 except that no coating material was used. As a result, the irreversible capacity was 36 mAhg- 1 . Next, a small battery was produced, and DC resistance was measured. The DC resistance was 12.1 ⁇ .

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

Abstract

La présente invention concerne un nouveau matériau de revêtement pour matériaux actifs d'électrode négative, possédant une capacité irréversible réduite et une résistance de batterie réduite. Cette invention est caractérisée en ce qu'elle porte sur un matériau de revêtement d'électrode négative pour batteries rechargeables au lithium-ion qui est représenté par la formule (1). Dans la formule (1), R3, R4 et R5 sont des groupes hydrocarbure en C1 -10 ou H, R1 et R2 contiennent au moins un groupe fonctionnel possédant des propriétés d'attracteur d'électrons, et n est un nombre de répétitions de l'unité structurelle. En résultat de la présente invention, une électrode négative à faible capacité irréversible et à faible résistance peut être obtenue. En outre, une batterie rechargeable au lithium-ion possédant une capacité élevée et d'excellentes caractéristiques de sortie peut être obtenue en résultat de l'application de ladite électrode négative à la batterie rechargeable au lithium-ion.
PCT/JP2014/052991 2014-02-10 2014-02-10 Matériau pour batteries au lithium Ceased WO2015118676A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2014/052991 WO2015118676A1 (fr) 2014-02-10 2014-02-10 Matériau pour batteries au lithium

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Application Number Priority Date Filing Date Title
PCT/JP2014/052991 WO2015118676A1 (fr) 2014-02-10 2014-02-10 Matériau pour batteries au lithium

Publications (1)

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WO2015118676A1 true WO2015118676A1 (fr) 2015-08-13

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PCT/JP2014/052991 Ceased WO2015118676A1 (fr) 2014-02-10 2014-02-10 Matériau pour batteries au lithium

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110790689A (zh) * 2019-11-11 2020-02-14 江西师范大学 一种1,1-二氟-2-异腈-乙基苯基砜类化合物的合成方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012074167A (ja) * 2010-09-28 2012-04-12 Sekisui Chem Co Ltd リチウムイオン二次電池用電極及びその製造方法、並びにリチウムイオン二次電池
JP2012079493A (ja) * 2010-09-30 2012-04-19 Sekisui Chem Co Ltd リチウムイオン二次電池用電極及びリチウムイオン二次電池
JP2013197078A (ja) * 2012-03-23 2013-09-30 Nippon Zeon Co Ltd 二次電池用多孔膜、二次電池用多孔膜スラリー組成物、二次電池用電極、二次電池用セパレータ及び二次電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012074167A (ja) * 2010-09-28 2012-04-12 Sekisui Chem Co Ltd リチウムイオン二次電池用電極及びその製造方法、並びにリチウムイオン二次電池
JP2012079493A (ja) * 2010-09-30 2012-04-19 Sekisui Chem Co Ltd リチウムイオン二次電池用電極及びリチウムイオン二次電池
JP2013197078A (ja) * 2012-03-23 2013-09-30 Nippon Zeon Co Ltd 二次電池用多孔膜、二次電池用多孔膜スラリー組成物、二次電池用電極、二次電池用セパレータ及び二次電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110790689A (zh) * 2019-11-11 2020-02-14 江西师范大学 一种1,1-二氟-2-异腈-乙基苯基砜类化合物的合成方法
CN110790689B (zh) * 2019-11-11 2022-04-01 江西师范大学 一种1,1-二氟-2-异腈-乙基苯基砜类化合物的合成方法

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