WO2012063286A1 - Batterie secondaire - Google Patents

Batterie secondaire Download PDF

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Publication number
WO2012063286A1
WO2012063286A1 PCT/JP2010/006601 JP2010006601W WO2012063286A1 WO 2012063286 A1 WO2012063286 A1 WO 2012063286A1 JP 2010006601 W JP2010006601 W JP 2010006601W WO 2012063286 A1 WO2012063286 A1 WO 2012063286A1
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WO
WIPO (PCT)
Prior art keywords
secondary battery
battery according
separator
nonwoven fabric
ceramic material
Prior art date
Application number
PCT/JP2010/006601
Other languages
English (en)
Japanese (ja)
Inventor
中島　潤二
Original Assignee
三菱重工業株式会社
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 三菱重工業株式会社 filed Critical 三菱重工業株式会社
Priority to PCT/JP2010/006601 priority Critical patent/WO2012063286A1/fr
Publication of WO2012063286A1 publication Critical patent/WO2012063286A1/fr

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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
    • 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
    • H01M50/44—Fibrous 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
    • H01M50/409—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
    • H01M50/429—Natural 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
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • 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
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • 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 secondary battery excellent in performance and safety.
  • a battery is a device that converts the chemical energy of a chemical substance inside into electrical energy through an electrochemical redox reaction.
  • portable electronic devices such as electronics, communications, and computers.
  • mobiles such as electric vehicles and stationary equipment for power load leveling systems. It is expected to be put into practical use and is becoming an increasingly important key device.
  • lithium-ion secondary batteries have brought great spread.
  • This lithium ion secondary battery uses a positive electrode having a lithium-containing transition metal composite oxide as an active material and a material capable of inserting and extracting lithium, such as lithium metal, lithium alloy, metal oxide, or carbon.
  • the main components are a negative electrode, an electrolyte, and a separator.
  • lithium ions emitted from a lithium metal composite oxide used as a positive electrode during initial charging move to a graphite electrode used as a negative electrode and are inserted between the graphite electrodes.
  • a thin film layer is formed on the surface of the graphite negative electrode.
  • Such a layer is called a SEI (Solid-Electrolyte-Interface) layer.
  • the SEI layer serves as an ion tunnel and allows only lithium ions to pass through.
  • the lithium ions again do not side-react with the graphite negative electrode or other substances, and the amount of lithium ions in the electrolyte is reversibly maintained, ensuring stable charge / discharge.
  • gases such as CO, CO 2 , CH 4 , C 2 H 6 are generated during the above-described SEI formation reaction due to decomposition of the carbonate-based organic solvent, This causes the problem that the thickness of the battery expands during charging.
  • the SEI layer gradually collapses as time passes during high temperature storage, and the side reaction in which the exposed negative electrode surface reacts with the surrounding electrolyte continues. Will occur.
  • Patent Document 1 Japanese Translation of PCT Publication No. 2009-507353
  • the present invention has been made to solve these problems, and the problem is that it is particularly excellent in performance, can simultaneously improve capacity and high output performance, and can expand the specification temperature range. Furthermore, it is an object of the present invention to provide a battery having excellent safety because an internal short circuit hardly occurs without contracting the separator.
  • the secondary battery of the present invention basically has a separator carrying a material containing a ceramic material and a phosphorus element in a nonwoven fabric, and the content ratio of the ceramic material is 50 wt% or more and 96 wt% or less,
  • the ceramic material is Al 2 O 3 , SiO 2 , TiO 2 , ZrO 2 , BaTiO 3 , AlPO 4 , ZrPO 4 , AlF 3 .
  • it is characterized by containing a polymer fiber having cellulose or an acrylic group.
  • the nonwoven fabric material is characterized by comprising materials such as PET (polyethylene terephthalate), PP (polypropylene), PPS (polyphenylene sulfite), mica (mica) and the like.
  • the capacity and high output performance can be improved at the same time, the specification temperature range can be expanded, and the separator is not shrunk, internal short circuit is less likely to occur, and it is safer and prevents copper damage.
  • a battery having a long life can be obtained.
  • the battery of the present invention high output and high capacity can be achieved at the same time, copper damage is suppressed, and the life is improved by being excellent in liquid retention. Further, safety can be improved because the temperature rise in the battery can be suppressed, it is flame retardant and non-flammable, and it does not shrink at high temperatures like a film, thereby preventing a short circuit. Furthermore, even if the battery itself is exposed to a high temperature, safety can be ensured by suppressing ion migration and cutting off the current by vitrification or the like.
  • charging and discharging can be stably performed even in a high operating voltage region (4.45 V or more).
  • This battery has a high voltage and a high capacity, can exhibit excellent charge / discharge performance, life, and rate performance (output characteristics), and can be used without problems even under high voltage and high temperature storage. Furthermore, since generation
  • FIG. 1 is a schematic configuration diagram of a separator of the present invention.
  • FIG. 2 is a table summarizing the battery conditions of this example.
  • FIG. 3 is a table showing the performance of the battery in each example of this example.
  • the separator which is the gist of the present invention is formed by supporting at least a nonwoven material 1 with a ceramic material 2 and a material 3 containing a phosphorus element.
  • the film-like separator does not shrink and short-circuit internally, and is flame retardant and non-flammable, thereby improving safety.
  • the diffusion rate is improved when ions move on the ceramic surface, and high output and rapid charging can be realized.
  • the separator has flame retardancy or nonflammability and does not shrink at high temperatures, a battery having excellent safety can be obtained.
  • the specification temperature range is expanded, and further, it relates to a lithium ion secondary battery or sodium ion secondary battery separator having excellent life characteristics, and a lithium ion secondary battery or sodium ion secondary battery including the separator. .
  • the positive electrode contains an active material capable of inserting and removing lithium ions or sodium ions.
  • active material lithium nickel manganate, lithium manganate, lithium nickelate, nickel cobalt lithium manganate, lithium manganese phosphate, lithium iron manganate, lithium manganese titanate and their modified products (coinciding with metals such as aluminum and magnesium) And composite oxides such as those using sodium instead of lithium.
  • those containing manganese are preferable.
  • PVdF, PTFE, P (VdF / HFP) and modified acrylonitrile rubber particle binder are soluble in carboxymethylcellulose (CMC) and soluble It may be combined with a modified acrylonitrile rubber (such as BM-720H manufactured by Nippon Zeon Co., Ltd.).
  • CMC carboxymethylcellulose
  • BM-720H modified acrylonitrile rubber
  • acetylene black, ketjen black, and various graphites may be used alone or in combination.
  • the negative electrode includes an active material capable of inserting and removing lithium ions or sodium ions.
  • the active material metallic lithium, various natural graphites and artificial graphite, silicon-based composite materials such as silicide, silicon oxide-based materials, titanium alloy-based materials, and various alloy composition materials can be used.
  • As a binder from the viewpoint of improving the lithium ion acceptability, SBR and a modified product thereof are used in combination with a cellulose resin such as CMC and added in a small amount.
  • acrylic resin, PVdF, PTFE or P (VdF / HFP) is used. It is more preferable that
  • the lithium salts include LiPF 6 , LiBF 4 , LiClO 4 , LiSbF 6 , LiAsF 6 , LiCF 3 SO 3 , LiN (SO 2 CF 3 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , One or two selected from the group consisting of LiC (SO 2 CF 3 ) 3 , LiN (SO 3 CF 3 ) 2 , LiC 4 F 9 SO 3 , LiAlO 4 , LiAlCl 4 , LiCl, LiI, LiBETI, LiTFS
  • the above can be mixed and used.
  • the concentration of the lithium salt is preferably 0.01 mol / l or more and lower than the saturated state.
  • ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), fluorinated ethylene carbonate (FEC), trifluoromethylcyclohexane (TFMCH), bistrifluoromethanesulfonylimide (TFSI), succinonitrile (SN), fluorinated phosphonitrile trimer and the like can also be used.
  • vinylene carbonate VC
  • CHB cyclohexylbenzene
  • PS propane sultone
  • PRS propylene sulfite
  • ES ethylene sulfite
  • a lithium salt or a sodium salt having a low lattice energy, a high degree of dissociation, an excellent ionic conductivity, and a good thermal stability and oxidation resistance.
  • the present invention is not limited to the examples shown below.
  • the following batteries were allowed to stand for a certain period of time after injecting the electrolyte in a dry air environment, and then subjected to a precharge process for about 20 minutes at a current corresponding to 0.1 C. A process of leaving aging in a 60 ° C. environment for 1 day is assumed.
  • Example 1 In Example 1, 10% by weight of propylene carbonate (PC), 10% by weight of fluorinated ethylene carbonate (FEC), 60% by weight of dimethyl carbonate (DMC), and 15% by weight of succinonitrile (SN) as organic solvents Lithium bistrifluoromethanesulfonylimide (LiTFSI) was used in a mixed solvent of 5% by weight, and LiPF 6 was dissolved as a lithium salt at 1 mol / L to obtain an electrolyte for a lithium ion battery. However, it is not limited to this composition.
  • PC propylene carbonate
  • FEC fluorinated ethylene carbonate
  • DMC dimethyl carbonate
  • SN succinonitrile
  • LiTFSI Lithium bistrifluoromethanesulfonylimide
  • the positive electrode uses LiMnO 2 formed on an Al foil. At the time of forming the positive electrode, an appropriate amount of each of acrylene black as a conductive agent and an acrylic resin as a binder is mixed.
  • the negative electrode is made of a copper foil formed by mixing half of artificial graphite and natural graphite. When forming the negative electrode, an appropriate amount of styrene butadiene rubber resin (SBR) and a thickener cellulose (cmc) are applied and mixed as a binder.
  • SBR styrene butadiene rubber resin
  • cmc thickener cellulose
  • the separator is a coating material in which the skeleton of the nonwoven fabric 1 is PET fiber, and ⁇ -Al 2 O 3 is mixed as a ceramic material 2 with an acrylic resin (for example, BM-520B manufactured by Nippon Zeon Co., Ltd.) at a 96: 4 weight ratio.
  • the non-woven fabric is impregnated with AlPO 4 which is phosphorus-containing material 3 having a weight 1/7 of the weight of Al 2 O 3 and dispersed, and heated to remove the solvent.
  • Example 2 In Example 1, the nonwoven fabric 1 is replaced with PET, and fibers made of PP are used.
  • Example 3 In Example 1, the nonwoven fabric 1 is replaced with PET and fibers of PPS material are used.
  • Example 4 the nonwoven fabric 1 is made of mica (mica) material instead of PET.
  • mica mica
  • Neobest manufactured by Olivest Co., Ltd. is used.
  • Example 5 In Example 1, instead of Al 2 O 3 which is the ceramic material 2, SiO 2 is used.
  • Example 6 (Example 6) In Example 1, anatase TiO 2 is used in place of Al 2 O 3 which is the ceramic material 2.
  • Example 7 In Example 1, ZrO 2 is used in place of Al 2 O 3 which is the ceramic material 2.
  • Example 8 In Example 1, BaTiO 3 is used instead of Al 2 O 3 which is the ceramic material 2.
  • Example 9 In Example 1, in place of the Al 2 O 3 is a ceramic material 2, using AlPO 4, a solid powder and only AlPO 4.
  • Example 10 (Example 10) In Example 9, ZrPO 4 is used instead of AlPO 4 .
  • Example 11 In contrast to Example 1, a material obtained by impregnating a paint in which AlF 3 is added to 1/10 weight of Al 2 O 3 weight is used.
  • Example 12 In Example 1, the nonwoven fabric 1 is entangled with cellulose fibers, and the average pore diameter before the cellulose is used is 0.6 ⁇ m, and the average pore diameter is 0.2 ⁇ m.
  • the hole diameter is not limited to this.
  • Example 13 In Example 1, the ratio of Al 2 O 3 and acrylic resin was 50:50 by weight.
  • Example 1 Comparative Example 1 In Example 1, the ratio of Al 2 O 3 and acrylic resin was 49:51 by weight.
  • Example 2 (Comparative Example 2) In Example 1, the ratio of Al 2 O 3 and acrylic resin was 97: 3 by weight.
  • Example 3 (Comparative Example 3) In Example 1, a separator having the same thickness and a PE film was used.
  • Example 1 it was confirmed that the positive electrode obtained the same tendency with other materials regardless of LiMnO 2 . The same applies to the negative electrode.
  • FIG. 2 shows a table summarizing the battery conditions of this example.
  • the battery of the present invention also operated at ⁇ 40 ° C., but it does not have the structure of the present invention, such as a comparative example, a structure that does not contain phosphorus, such as no phosphorus, or that uses a film separator. It did not work at -40 ° C.
  • the secondary battery according to the present invention has excellent performance and is useful as a highly safe and high-performance power source.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Cell Separators (AREA)
  • Secondary Cells (AREA)

Abstract

Les films de séparation de PE ou PP qui sont utilisés de façon habituelle s'oxydent et se dégradent. Le risque pour qu'au final, les propriétés isolantes soient réduites ou que les performances de durée de vie diminuent, n'a pas été résolu. En outre, avec des configurations classiques de batterie, un compromis a été trouvé entre capacité et rendement, c'est pourquoi il est difficile d'obtenir un rendement élevé. Dans un système électrolytique, le problème à résoudre est qu'en résultat à la dépendance d'un électrolyte à la température, les performances à basse température sont dégradées de sorte que les performances souhaitées ne puissent pas être obtenues. En outre, après l'expansion des applications spécifiques, une recharge rapide est également souhaitée. Dans le séparateur selon la présente invention, par la configuration de celui-ci de façon à ce qu'il supporte un matériau contenant un matériau céramique et du phosphore élémentaire dans un tissu non tissé, il est possible de maintenir en continu une isolation dans un environnement prévu et d'améliorer la sécurité.
PCT/JP2010/006601 2010-11-10 2010-11-10 Batterie secondaire WO2012063286A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2010/006601 WO2012063286A1 (fr) 2010-11-10 2010-11-10 Batterie secondaire

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2010/006601 WO2012063286A1 (fr) 2010-11-10 2010-11-10 Batterie secondaire

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WO2012063286A1 true WO2012063286A1 (fr) 2012-05-18

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104103793A (zh) * 2014-06-05 2014-10-15 广东工业大学 一种阻燃有机/无机复合隔膜的制备方法
CN104143616A (zh) * 2014-07-09 2014-11-12 浙江金美能源科技有限公司 锂离子电池的隔离膜的涂布浆料、隔离膜及其制备方法
JP2015215977A (ja) * 2014-05-08 2015-12-03 エス・イー・アイ株式会社 リチウム二次電池

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001015160A (ja) * 1999-04-30 2001-01-19 Ohara Inc ガラスセラミックス複合電解質、及びリチウム二次電池
JP2005536860A (ja) * 2002-08-27 2005-12-02 デグサ アクチエンゲゼルシャフト リチウムバッテリー用のイオン伝導性バッテリーセパレータ、その製造方法及びその使用
JP2006507636A (ja) * 2002-11-26 2006-03-02 デグサ アクチエンゲゼルシャフト 電気化学的セルのための長時間安定性のセパレータ
JP2009507353A (ja) * 2005-09-05 2009-02-19 エボニック デグサ ゲーエムベーハー 改善された取り扱い性を有するセパレータ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001015160A (ja) * 1999-04-30 2001-01-19 Ohara Inc ガラスセラミックス複合電解質、及びリチウム二次電池
JP2005536860A (ja) * 2002-08-27 2005-12-02 デグサ アクチエンゲゼルシャフト リチウムバッテリー用のイオン伝導性バッテリーセパレータ、その製造方法及びその使用
JP2006507636A (ja) * 2002-11-26 2006-03-02 デグサ アクチエンゲゼルシャフト 電気化学的セルのための長時間安定性のセパレータ
JP2009507353A (ja) * 2005-09-05 2009-02-19 エボニック デグサ ゲーエムベーハー 改善された取り扱い性を有するセパレータ

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015215977A (ja) * 2014-05-08 2015-12-03 エス・イー・アイ株式会社 リチウム二次電池
WO2015170785A3 (fr) * 2014-05-08 2015-12-30 エス・イー・アイ株式会社 Batterie secondaire au lithium
CN104103793A (zh) * 2014-06-05 2014-10-15 广东工业大学 一种阻燃有机/无机复合隔膜的制备方法
CN104143616A (zh) * 2014-07-09 2014-11-12 浙江金美能源科技有限公司 锂离子电池的隔离膜的涂布浆料、隔离膜及其制备方法

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