WO2007066639A1 - Batterie secondaire au lithium - Google Patents

Batterie secondaire au lithium Download PDF

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Publication number
WO2007066639A1
WO2007066639A1 PCT/JP2006/324225 JP2006324225W WO2007066639A1 WO 2007066639 A1 WO2007066639 A1 WO 2007066639A1 JP 2006324225 W JP2006324225 W JP 2006324225W WO 2007066639 A1 WO2007066639 A1 WO 2007066639A1
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WO
WIPO (PCT)
Prior art keywords
positive electrode
negative electrode
active material
battery
electrode active
Prior art date
Application number
PCT/JP2006/324225
Other languages
English (en)
Japanese (ja)
Inventor
Tsuyoshi Hatanaka
Hideaki Fujita
Original Assignee
Matsushita Battery Industrial Co., Ltd.
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 Matsushita Battery Industrial Co., Ltd. filed Critical Matsushita Battery Industrial Co., Ltd.
Publication of WO2007066639A1 publication Critical patent/WO2007066639A1/fr

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Classifications

    • 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
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2300/0025—Organic electrolyte
    • 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 002-tium secondary battery Due to its high degree of energy, the 002-tium secondary battery has become widespread as a source for consumer equipment, for example, mobile phones, sons, and other information devices.
  • secondary batteries are also nowadays attracting attention as a power source for electric vehicles, especially for electric vehicles ().
  • the secondary battery for mobile use will be put into practical use.
  • a secondary battery for operation needs to generate a large current that is ten times as high as that of a general consumer lithium secondary battery at a time rate of 20 to 40C, though it is a short time. In order to obtain higher output power, it is necessary to suppress the resistance of the rechargeable lithium battery.
  • a high-power pond for use is required to discharge at a large current of 20 to 40C at a time rate of around 0, although the time is around 0.
  • a high-power pond for use is required to discharge at a large current of 20 to 40C at a time rate of around 0, although the time is around 0.
  • 0007 Cations such as thium compounds, are used as positive electrodes.
  • a possible way to improve the electrons when used as a quality is to include acetyl black or ketchin black as a conductive material in the positive electrode.
  • 009 including positive electrode current collector and positive electrode formed thereon, negative electrode A positive electrode, a negative electrode formed on the positive electrode, a battery disposed between the positive electrode and the negative electrode, and a solvent containing a thiium salt dissolved in the solvent.
  • a positive electrode 7 to 3 a positive electrode 35 to 55, and a concentration of the thiium salt in the range .multidot.2 o to 2 o. In the 001 0 thium ion secondary battery, it is preferable that it is 35 to 50 of the negative electrode.
  • FIG. 12 is a graph showing an example of the characteristics of a thium ion secondary battery.
  • 3 is a graph showing the relationship with the concentration output property of the contained thium salt measured in 2.
  • 3 is a graph showing the relationship between the output characteristics of the positive electrode measured in 2 3.
  • 43 is a graph showing the relationship between the output characteristics of tin black in the positive electrode layer, measured in 4 3.
  • 5 is a graph showing the relationship between the output characteristics of the negative electrode measured at 54.
  • the thium-ion secondary battery of the present invention includes a positive electrode current collector and a positive electrode formed thereon, a negative electrode current collector and a negative electrode formed thereon, and a battery disposed between the positive electrode and the negative electrode. Containing a metal case containing solvent, and a solvent containing thiium salt dissolved in the solvent. It is equipped with. , Positive electrode and. , The positive electrode occupies 7 to 3. It is 35 to 55. As described above, the concentration of the thiium salt in the positive electrode, the concentration of the non-medium thium salt in the positive electrode, and the amount of the agent contained in the positive electrode can be optimized to suppress the addition of the reaction. I can do it. Therefore, a battery having excellent output performance can be obtained.
  • the positive electrode also contains a high concentration of thion ions. Therefore, when the discharge is carried out at, the difference between the content of thiium ion and the content of nearby thiium ion becomes large, and the content of thium ion from the surface to the surface becomes faster.
  • the concentration of thium salt is ⁇ 2 ⁇ ⁇ o.
  • the amount of the 006 agent is 7 to 3, and preferably 7 to 3. If the amount of agent is less than that of positive electrode 7, the output performance is improved. The fruit is obtained. When the amount of the agent is larger than that of the positive electrode 3, the amount of the substance contained in the positive electrode is large, and the amount of thium ion that can reach the positive electrode surface is reduced. Therefore, the output performance is reduced. Included in 01717 are, for example, acetyl black, ketch black, fan black, lap black, zabla, and other bombs, carbon, and metals.
  • the reaction at the negative electrode may be delayed and the battery power may decrease. Therefore, it is preferable to increase the output of the negative electrode by optimizing the negative electrode.
  • the negative electrode is preferably 35 to 50, and more preferably 35 to 45. In the thium-ion secondary battery, it has a negative polarity of 30. As a matter of fact, the negative electrode is larger than the negative electrode in consumer lithium ion secondary batteries. For this reason, the movement of thium ions at the negative electrode is easy, and the thium ions move from the negative electrode to the positive electrode during discharge. Therefore, it is possible to further improve the battery performance.
  • the titanium salt conventionally used in the field can be used.
  • P B etc. can be used.
  • thiium oxide for quality, it is possible to use thiium oxide in the field.
  • Such compounds include, for example, thallium compounds, thimium compounds, and thallium compounds. Above all, thirium oxide is preferred because it is relatively inexpensive.
  • Quality of 7 to 2 is preferred.
  • the quality is 7, the amount of fine powder increases and it becomes difficult to handle the positive electrode quality. If the quality exceeds 20, the reaction product may decrease and the output may decrease. In addition, in the case of high-powered ponds, the design will be thin. this Therefore, the quality of the positive electrode is large and the production yield may be reduced.
  • 002 is, in the field, reversibly sucking and
  • capable materials include metals, carbon materials, compounds and elementary compounds.
  • Examples of the constituent metals include metals capable of forming alloys such as () and (S). Instead of metal, a metal element capable of forming an alloy can be used.
  • Examples of the raw material include various types, shavings, upper, carbon, spherical, various types, and raw materials.
  • Examples of the elementary compound include SO (05 .95), and elemental compounds, compounds and bodies. It should be noted that the gold, the compound, and the S part in the body are replaced by at least one element selected from the group consisting of Bo Co Ca CC eba, W, Z, C, and S. For example,
  • the negative electrode is a body such as S S, an elemental compound, and / or a negative electrode.
  • 002 Quality, 7 to 2 is preferred.
  • the quality reaches 7%, the amount of fine powder increases and it becomes difficult to handle the negative electrode quality. If the quality exceeds 20, the product of the negative electrode quality may decrease and the output performance may decrease. For high-powered ponds, the design will be thin. For this reason, the quality of the negative electrode is large and the production yield may be reduced.
  • 024 it may be composed of only the negative electrode material. Also, it may be included.
  • the body such as S, the element compound, the compound, and the fact that it adheres to the current collector does not contain only the negative electrode material.
  • the negative electrode can be controlled by adjusting the deposition amount, the deposition time, and / or the deposition degree when the negative electrode quality is negotiated on the current collector.
  • the positive electrode and the agent may contain
  • P Bohoffiden
  • P Terafuchi
  • the P positive electrode is 2 to 5 and the P positive electrode is 7 to 7.
  • P and tin butadiene (SBR) can be used as the negative electrode.
  • SBR tin butadiene
  • the negative electrode of P is 5 to 2 and the negative electrode of S R is from 5 to 5.
  • the public materials can be used in the field as the material for the current collector, the negative electrode current collector and the electrode.
  • the solvent contained can be a public solvent in the field.
  • the quality is mixed with an agent for imparting.
  • This mixture can be mixed with a solution of and a dispersion of to obtain a positive electrode. At this time, it is adjusted so that it becomes 45 to 65 of the space.
  • a methices (CC) can be used.
  • the CC of the CC solution can be, for example:
  • the obtained strip is applied to, for example, a positive electrode current collector surface made of an aluminum foil, And then, for example, drying through a furnace adjacent to
  • the positive electrode can be obtained by rolling with a press. Incidentally, at this time, by changing the rolling force, the value of the positive electrode can be adjusted to a predetermined value. It is possible to do so by using the body of the device, for example, the data, the data, etc. , For example, can be done by pressing.
  • As a material for forming the current collector for example, an aluminum foil can be used.
  • 003 for example, can be produced as follows.
  • This soot is processed, for example, on the surface of the negative electrode current collector, and then dried, for example, through a furnace adjacent to, to obtain. By rolling this, a negative electrode can be obtained. Note that, similarly to the above, by changing the force of the negative electrode at this time, it is possible to adjust it to a predetermined value.
  • poles As in the case of poles, one can use methices and that can.
  • the body of the chair for example, a printer, a printer, or the like. However, for example, it can be done by push or the like.
  • the material for forming the pole current collector can be used.
  • 003 and can be determined, for example, by mercury porosimetry.
  • 0032 for example, can be assembled as follows.
  • a set is placed between the positive electrode and the negative electrode obtained as described above to obtain a laminate. Then, get Then, place it in the battery case, and seal the battery case to complete the battery.
  • a case made of aluminium a case made of iron with a plated inner surface, or a case made of aluminium, may be used as the case. It may have a misaligned shape such as a case, cylinder, or square shape.
  • the cross-section of the group is the same as that of the battery case, but the shape of the positive electrode, the negative electrode, etc., in which the shape of the circle is selected, is selected from the materials conventionally used in the field. You can
  • the 003 pond can be evaluated, for example, as follows.
  • the battery is charged to a predetermined value (S a e Of Cage S C).
  • the pond is discharged for 0 for a time rate of C, and the discharge pond is brought to 30 state. This left pond is charged with the same (C) as the discharge. After that, the pond will be suspended for 30 minutes. After completing this condition, the above cycle is also applied at an hourly rate of 2C 5C C 20C 30C and 40C.
  • the quality of the composition is represented by Co
  • the coated powder was applied to the surface of the anode current collector (20) and dried. Then, a positive electrode was obtained by pressing so as to obtain 40 of the positive electrode.
  • the positive electrode had a length of 80 and a length of 2500.
  • the quality, a solution of methices (CC), and thimbulium (SBR) were mixed to obtain a negative electrode s.
  • the negative electrode material C C S R was 00: 0: 5.
  • the obtained 004 was applied to the surface of the current collector (0 is) of and dried.
  • a negative electrode was obtained by pressing so as to obtain 40 of the obtained negative electrode.
  • the size of the negative electrode was 85 and the length was 2650.
  • a pond was prepared using the obtained positive electrode and electrode.
  • a laminate was obtained by arranging a metal between the positive electrode and the negative electrode.
  • Chicabone was prepared by dissolving 6 Ht (P) in the solvent in which Mechicabone was mixed in 2 at each step.
  • the battery was tested and then jigged. Always first
  • the battery was activated by performing initial charge and then activated. The same applies to the other batteries of this embodiment and Embodiments 2 to 4. 004 I turned on the power as shown below. First, the battery was charged at a flow rate of 0.2 C at a battery pressure of 4.2. Then, the battery was discharged at a flow of 0.2C until the battery pressure dropped to 3 *, and then charged at a flow of 0.2C until the battery pressure became 4.2. This cycle was repeated 2 times, and the battery was charged up to 00 C and left in the environment C for 7 hours.
  • Batteries 2 to 4 were produced in the same manner as the batteries, except that the concentration of the thium salt was set to • 2 o, • 8, or 2 ⁇ o.
  • Comparison 2 was prepared in the same manner as the battery, except that the concentration of the thiium salt was set to • O o or 2.2 °.
  • the output performance was evaluated in the above-mentioned ponds of 005 cells and batteries ⁇ 4 and ⁇ 2, and the pond value was calculated. , 3 ⁇ 0.
  • this test was performed at 60 C and 25 C.
  • the reason for conducting the test at 60 OC depends on the control system, but is mainly used in the condition where OC is about 60.
  • the charging current reached a maximum value of 0C, and the charging was performed at 0C above 20C, and by adjusting the charging interval, the same amount of discharged electricity was charged.
  • the output was improved.
  • concentration of thium salt exceeded o, the output was slightly reduced, but sufficient output was maintained.
  • concentration of thium salt exceeds ⁇ , it is considered that the output is slightly decreased because the amount of thion ion is decreased.
  • the output level was significantly lower than that of Battery 2 in which the concentration of thium salt was ⁇ 2 o.
  • the reason for this is that when the thixium content is o, when the battery is discharged with a large current, the battery pressure drops abruptly at 0 after the beginning of discharge, and the property and note are lost. Is considered to be.
  • the thium salt is released from the liquid. Since it is expected to be below 20oC around the pond, it can be used for batteries containing such high concentration of thium salt. It is possible.
  • the concentration of the contained thium salt is 2 o to 2 o.
  • the positive electrode was changed.
  • the quality of the positive electrode current collection battery was the same as that of the battery. 005 (5 to 7)
  • Batteries 5 to 7 were prepared in the same manner as the battery by adjusting the force at the time of extension and adjusting the positive electrode to 350 or 55.
  • Comparisons 3 to 4 were prepared in the same manner as in the case where the positive electrode was adjusted to 30 or 60 by adjusting the elongation force.
  • the value of the 005 pond was determined in the same manner as the implementation. The results are shown in Fig. 3. The result of the battery (of: 40) is also shown in 3.
  • the output is excellent when it is in the range of ⁇ 60 from the positive electrode.
  • (2) is high, it is easy for thium ions to diffuse from the cathode to the positive electrode part, and therefore it is easy for thium ions to be supplied to the positive electrode surface.
  • the black fiber which is, also aggregates to a high density. At this time, the thium-iot contained in this will occur. Therefore, it is considered that the reason why the output power is large when the temperature is above 35 of the positive electrode is that the thium ion is easily scattered from the substance because the temperature is so high.
  • the amount of tin black (B) was changed. Even in the pond, the batteries had the same quality per positive electrode current collection.
  • Batteries 8 to 9 were prepared in the same manner as the battery, except that tin black was used as the positive electrode 7 or 3.
  • Comparisons 5 to 6 were made in the same manner as the battery, except that tin black was used as the positive electrode 6 or 5.
  • the batteries 40 to 9 and 5 to 6 were the positive electrodes.
  • the value of the 006 pond was determined in the same manner as the implementation. The results are shown in Fig. 4. In addition, 4 shows the result of the battery (0 of acetyl black).
  • the output performance is excellent when it is 7 to 3 of acetyl black ().
  • the effect of improving output performance cannot be obtained. There are 3 and many of them. For this reason, the amount of the liquid retained in is large, and the amount of thium ions reaching the positive electrode surface is thought to decrease. Moreover, it is considered that when the temperature is high, it causes the generation of thionium on the positive electrode surface from the material.
  • the deterioration of the negative electrode causes deterioration of the negative electrode quality, and in some cases, there are problems caused by the deterioration of the negative electrode quality. For this reason, it is considered that the output performance decreased when the negative electrode was 55.
  • the negative electrode has a value of 35 to 50.
  • Ketchin Black was used, or when a mixture of Chin Black and Ketchin Black was used, the results similar to those of Examples 1 to 4 were obtained.
  • a thium ion secondary battery with excellent output performance could be obtained by setting the content of thium in the range of -2 o to 2 o and the positive electrode of 35 to 55.
  • the above-mentioned, 006-Am thium-ion secondary battery has excellent output performance, so it can be suitably used, for example, as a power source for electric vehicles and vehicles.

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

Abstract

La présente invention concerne une batterie secondaire au lithium comprenant un groupe de plaques d’électrodes incluant une électrode positive, une électrode négative et un séparateur disposé entre l’électrode positive et l’électrode négative ; un logement de batterie destiné à contenir le groupe de plaques d’électrodes ; et une solution électrolytique non aqueuse contenant un sel de lithium dissous dans un solvant non aqueux. L’électrode positive comprend une couche mixte d’électrode positive formée sur un collecteur d’électrode positive, et ladite couche mixte contient une matière active d’électrode positive et un agent conducteur. L’électrode négative comprend une couche de matière active d’électrode négative formée sur un collecteur d’électrode négative. Lorsqu’une telle batterie secondaire au lithium est utilisée pour un VEH ou analogue, il faut des caractéristiques de sortie élevée permettant une importante décharge de courant telle qu’un taux horaire de 20 à 40 C, même sur une courte période de temps telle qu’une dizaine de secondes. Dans la batterie secondaire au lithium, 7 à 13 % en poids de ladite couche mixte sont composés de l’agent conducteur, ladite couche mixte a une porosité de 35 à 55 % et la concentration en sel de lithium contenu dans la solution électrolytique non aqueuse va de 1,2 mol/l à 2 mol/l. En conséquence, les caractéristiques de sortie de la batterie secondaire au lithium sont améliorées.
PCT/JP2006/324225 2005-12-06 2006-12-05 Batterie secondaire au lithium WO2007066639A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005352305 2005-12-06
JP2005-352305 2005-12-06

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102856530A (zh) * 2011-06-30 2013-01-02 清华大学 锂离子电池
CN108780930A (zh) * 2016-01-13 2018-11-09 弗莱克斯电子有限责任公司 在高速率电池放电期间估计放电持续时间的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000149945A (ja) * 1998-11-10 2000-05-30 Hitachi Ltd リチウムイオン二次電池
JP2000235868A (ja) * 1998-10-29 2000-08-29 Toshiba Corp 非水電解液二次電池
WO2001091211A1 (fr) * 2000-05-24 2001-11-29 Mitsubishi Cable Industries, Ltd. Accumulateur au lithium et materiau actif d'electrode positive, plaque positive et leur procede de fabrication
JP2002025606A (ja) * 2000-07-10 2002-01-25 Toyota Central Res & Dev Lab Inc リチウム二次電池
JP2002151055A (ja) * 2000-08-28 2002-05-24 Nissan Motor Co Ltd リチウムイオン二次電池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000235868A (ja) * 1998-10-29 2000-08-29 Toshiba Corp 非水電解液二次電池
JP2000149945A (ja) * 1998-11-10 2000-05-30 Hitachi Ltd リチウムイオン二次電池
WO2001091211A1 (fr) * 2000-05-24 2001-11-29 Mitsubishi Cable Industries, Ltd. Accumulateur au lithium et materiau actif d'electrode positive, plaque positive et leur procede de fabrication
JP2002025606A (ja) * 2000-07-10 2002-01-25 Toyota Central Res & Dev Lab Inc リチウム二次電池
JP2002151055A (ja) * 2000-08-28 2002-05-24 Nissan Motor Co Ltd リチウムイオン二次電池

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102856530A (zh) * 2011-06-30 2013-01-02 清华大学 锂离子电池
CN108780930A (zh) * 2016-01-13 2018-11-09 弗莱克斯电子有限责任公司 在高速率电池放电期间估计放电持续时间的方法
CN108780930B (zh) * 2016-01-13 2021-09-07 弗莱克斯电子有限责任公司 在高速率电池放电期间估计放电持续时间的方法

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