[go: up one dir, main page]

WO2008041714A1 - DISPOSITIF DE charge ET Son procÉDÉ DE FABRICATION - Google Patents

DISPOSITIF DE charge ET Son procÉDÉ DE FABRICATION Download PDF

Info

Publication number
WO2008041714A1
WO2008041714A1 PCT/JP2007/069315 JP2007069315W WO2008041714A1 WO 2008041714 A1 WO2008041714 A1 WO 2008041714A1 JP 2007069315 W JP2007069315 W JP 2007069315W WO 2008041714 A1 WO2008041714 A1 WO 2008041714A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
storage device
positive electrode
charge
voltage
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/JP2007/069315
Other languages
English (en)
Japanese (ja)
Inventor
Masakazu Tanahashi
Hiroe Kondo
Hideya Yoshitake
Tetsuo Yamada
Shinichi Ishitobi
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.)
Ube Corp
Original Assignee
Ube Industries 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
Priority claimed from JP2006272318A external-priority patent/JP4863001B2/ja
Priority claimed from JP2006272317A external-priority patent/JP4863000B2/ja
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Publication of WO2008041714A1 publication Critical patent/WO2008041714A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/46—Accumulators structurally combined with charging apparatus
    • 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 power storage device, a power storage system, an electronic device using the same, and a power system that have a high voltage, a large capacity, and high reliability in a charge / discharge cycle.
  • a power storage device using a non-aqueous electrolyte there are a lithium ion secondary battery and an electric double layer capacitor.
  • lithium ion secondary batteries a lithium-containing transition metal oxide is used for the positive electrode, and a graphite-based carbon compound capable of intercalating lithium is preferably used for the negative electrode.
  • a non-aqueous electrolyte containing is used.
  • lithium-ion secondary batteries usually use a lithium-containing transition metal oxide for the positive electrode, the lithium-ion secondary battery can realize charging and discharging at a high voltage, resulting in a high-capacity battery.
  • the positive and negative electrode active materials themselves occlude and desorb lithium ions, resulting in early deterioration of the charge / discharge cycle.
  • the electric double layer capacitor is composed of a polarizable electrode mainly composed of activated carbon for both the positive electrode and the negative electrode, it enables rapid charge and discharge even though the capacity is low, and in the charge and discharge cycle. High level and reliability can be secured.
  • Patent Document 1 proposes a special carbon material used as an electrode material for an electric double layer capacitor and a method for manufacturing the same.
  • Patent Document 2 the half-value width in the X-ray diffraction of the (002) peak is 0.5 to 5.0.
  • An electric double layer capacitor containing the graphite-based carbon material as the main component of both the positive electrode and the negative electrode has been proposed, but as shown in the examples, after the electric double layer capacitor was fabricated, Instead of activation treatment, use a high voltage of 3.8V for 20 minutes to 5 hours.
  • Patent Document 3 uses an electric power in which boron-containing graphite obtained by heat treatment of a carbon material containing boron or a boron compound is used as the positive electrode carbon material, and activated carbon is used as the negative electrode carbon material. Double layer capacitors have been proposed. Patent Document 3 does not disclose details of the force S for estimating the anion intercalation reaction at the positive electrode and the charge / discharge process. Details regarding physical properties such as specific surface area of boron-containing graphite have also been clarified!
  • Patent Document 4 also proposes an electric double layer capacitor using graphite as a positive electrode active material and using graphite or activated carbon as a negative electrode active material! It is said that it is expressed by the adsorption and desorption of ions at the negative electrode.
  • Patent Document 1 Japanese Patent Laid-Open No. 10-199767
  • Patent Document 2 JP 2002-151364 A
  • Patent Document 3 Japanese Unexamined Patent Application Publication No. 2004_134658
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-294780
  • the present invention relates to a conventional lead battery, lithium ion secondary battery, nickel metal hydride secondary battery, electric
  • An object of the present invention is to provide an electricity storage device that can replace a multilayer capacitor and the like, has a substantially large storage capacity and energy capacity, and has high reliability in a charge / discharge cycle.
  • the present invention relates to a first mode in which the negative electrode is reversely charged with a positive charge during complete discharge (hereinafter referred to as mode A), and charging with a negative charge remaining without discharging the negative electrode during complete discharge. It includes two embodiments of the second embodiment (hereinafter referred to as embodiment B).
  • a of the present invention is characterized by the following matters.
  • An electricity storage device including a positive electrode and a negative electrode containing a carbonaceous active material, wherein the electrical charging process at the positive electrode comprises the adsorption process of ayuon in the low voltage region and the intercalation process in the high voltage region.
  • a storage device wherein the negative electrode is reversely charged with a positive charge when fully discharged.
  • the positive electrode and the negative electrode are set so that the negative electrode potential exceeds the irreversible reaction potential at the negative electrode before the positive electrode reaches the maximum allowable amount of electricity during initial charging,
  • the operating voltage range of the negative electrode is expanded by 10% or more of the operating voltage range based on cation adsorption inherent in the negative electrode, as described in any one of 1 to 3 above Power storage device.
  • the cumulative chargeable capacity of the negative electrode contributes to the cation adsorption inherent in the negative electrode. 4.
  • a graphite material is used as an active material of the positive electrode
  • the positive electrode potential during charging is 5.2 Vvs. Li +
  • the power storage device according to any one of 1 to 9 above, which is used in a range not exceeding / Li.
  • a method for producing an electricity storage device comprising a positive electrode and a negative electrode containing a carbonaceous active material
  • a method for producing an electricity storage device comprising performing at least one open charge and open charge at a voltage at which an irreversible reaction occurs at the negative electrode.
  • aspect B of the present invention is characterized by the following matters.
  • An electricity storage device comprising a positive electrode and a negative electrode containing a carbonaceous active material, wherein the electrical charging process at the positive electrode comprises an adsorption process of ayuons in a low voltage region and an intercalation process in a high voltage region.
  • An electricity storage device wherein the negative electrode is charged with a negative charge remaining without being discharged at the time of complete discharge.
  • the positive electrode and the negative electrode must be connected before the negative electrode reaches the maximum allowable amount of electricity during initial charging.
  • the positive electrode potential is set to exceed the irreversible reaction potential at the positive electrode
  • the electricity storage device which is produced by performing at least one open charge and open discharge at a voltage at which an irreversible reaction occurs at the positive electrode.
  • a graphite material is used as an active material of the positive electrode
  • the positive electrode potential during charging is 5.2 Vvs. Li +
  • a method for producing an electricity storage device comprising a positive electrode and a negative electrode containing a carbonaceous active material
  • the electrical charging process at the positive electrode shows the adsorption process of the ayuon in the low voltage region and the intercalation process in the high voltage region
  • the electrical charging at the negative electrode occurs due to the adsorption of 1S cations
  • the initial stage Set the capacities of the positive and negative electrode materials so that the positive electrode potential exceeds the irreversible reaction potential at the positive electrode before the negative electrode reaches the maximum allowable amount of electricity during charging.
  • a method for manufacturing an electricity storage device comprising performing at least one open charge and open discharge at a voltage at which an irreversible reaction occurs at the positive electrode.
  • the present invention while maintaining the characteristic of high-speed charge / discharge characteristic of a non-aqueous electric double layer capacitor, it can be used at a higher voltage than a conventional electric double layer capacitor. It is possible to provide an electricity storage device with high reliability in a charge / discharge cycle in which the electricity storage capacity and energy capacity that can be used qualitatively are large.
  • the charging / discharging process is a two-stage process of reversible adsorption and reversible intercalation of the cation on the positive electrode active material, so that the decomposition reaction of the electrolytic solution is suppressed during device use.
  • a high-capacity storage device particularly a high-energy storage device, using the intercalation region.
  • the electricity storage device of the present invention does not fall within the category of an electric double layer capacitor in which the electrolyte is adsorbed on the polarizable electrode and develops capacity, but can be charged / discharged more rapidly than a conventional battery.
  • the negative electrode is reversely charged with a positive charge during complete discharge. This means that in addition to the electric capacity expressed by the adsorption capability inherent in the negative electrode, an electric capacity corresponding to the positively charged positive charge can be stored and discharged. For this reason, according to this aspect, a high capacity
  • activated carbon having a large surface area is also used in one method. Since the surface area and the electrode density are in a contradictory relationship, the power storage device that emphasizes the capacity per volume is important. This is probably the best way!
  • a method for modifying a low surface area activated carbon to an activated carbon for a capacitor by performing an electrochemical operation in the assembled device is known as a nanogate capacitor (JP 2002-0225867, etc.).
  • the modification of the activated carbon in the nanogate capacitor is to expand the carbon layer by intercalating ions between the coater carbon layers during charging, and use the expanded carbon layer as an ion adsorption site.
  • the increase in the capacity of the negative active carbon of this embodiment A does not involve the modification of the surface area by adding an electrochemical treatment to the activated carbon. It increases the ion adsorption capacity of activated carbon, which expands the adsorption capacity not only to cations but also to anions, in other words, the adsorption utilization rate of ions.
  • the activated carbon may be a commercially available activated carbon, and the capacity balance between the positive electrode and the negative electrode may be adjusted.
  • the activated carbon is simply performed as a device stabilization process! /, Capacity of activated carbon as a conventional negative electrode active material by controlling the conditions of open charge Can be raised from 20% to 50%.
  • the negative electrode is in a state of being charged with a negative charge remaining without being discharged, so the isoelectric point is shifted to the low potential side, and as a result, the positive electrode is The transition voltage that changes from V-ion adsorption to intercalation increases. Therefore, the power storage device of the present aspect B has a high operating voltage and a capacity in a high voltage range that is pulled up. Furthermore, it is possible to reduce the load of anion intercalation on the positive electrode in the low voltage range that is not practically used.
  • the electricity storage device of the present embodiment B has high voltage, high capacity, and good cycle characteristics.
  • the power storage device of the present embodiment B can obtain a high operating voltage of 1.75V power, 3.5V, etc.
  • the power storage device of the present embodiment B can be used in a field where rapid charge and discharge is performed at a high voltage.
  • the chair features are effective, and can be used, for example, as an engine starter power supply or a HEV storage device.
  • the power required for a storage device for HEV that requires a voltage of 200V or higher Compared to conventional electric double layer capacitors, the number of devices in series is reduced by 40%. This not only has the effect of simplifying the booster circuit, but also has the merit of reducing the failure frequency because all energy in the series part cannot be obtained if one device fails because of the series.
  • FIG. 1-1 is a diagram showing an electricity storage device before charging.
  • (A) is a schematic diagram for showing the relationship between positive and negative electrode capacities, potentials, and voltages, where the horizontal axis represents the potential and the vertical axis represents the capacitance (dQ / dV).
  • (B) is a schematic diagram of a battery configuration for showing a charge balance between a positive electrode and a negative electrode.
  • FIG. 1-2 A diagram showing an electricity storage device in a state of being charged. Refer to the explanation in Fig. 11 for the explanation of (A) and (B).
  • FIG. 1-3 A diagram showing an electricity storage device in a state where the negative electrode has reached a chargeable integrated capacity.
  • (A) and (B) see the explanation of Fig. 11.
  • FIG. 1-4 is a diagram showing an electricity storage device in a state where an irreversible reaction occurs due to overcharge.
  • (A) and (B) see the explanation of Fig. 11.
  • FIG. 1-5 It is a diagram showing an electricity storage device in a state of being discharged to an initial isoelectric point. Refer to the explanation of Fig. 11 for the explanation of (A) and (B).
  • FIG. 1-6 is a diagram showing the electricity storage device in a fully discharged state.
  • FIG. 11 For the explanation of (A) and (B), see the explanation of Fig. 11.
  • FIG. 1_7 A diagram showing an electricity storage device in a state where an irreversible reaction occurs due to the second overcharge! See the description of Figure 1-1 for an explanation of (A) and (B).
  • FIG. 1-8 is a diagram showing an electricity storage device that has been completely discharged after the second overcharge. See the description of Figure 11 for an explanation of (A) and (B).
  • Example A Draw a graph indicating the characteristics of the electricity storage device during the first and tenth charging in Example 1.
  • FIG. 1-11 This is a graph schematically showing the voltage dependence of capacitance in an actual device.
  • FIG. 1-13 Storage device when open charge / discharge is repeated to overcharge voltage in Example A-2 1-15] Diagram for explaining the limit charge potential and inter-terminal voltage of the storage device when in use It is. See the description of Figure 1-1 for an explanation of (A) and (B).
  • FIG. 2-1 is a diagram showing an electricity storage device before charging.
  • (A) is a schematic diagram for showing the relationship between positive and negative electrode capacities, potentials, and voltages, where the horizontal axis represents the potential and the vertical axis represents the capacitance (dQ / dV).
  • FIG. 2-1 is a schematic diagram of a battery configuration for showing a charge balance between a positive electrode and a negative electrode.
  • FIG. 2-2 is a diagram showing the electricity storage device in a state of being charged. For the explanation of (A) and (B), see the explanation of Figure 2-1.
  • FIG. 2-3] is a diagram showing the electricity storage device in a state where the accumulated capacity that can be charged by the positive electrode has been reached. See the description of Figure 21 for an explanation of (A) and (B).
  • FIG. 2-4 is a diagram showing an electricity storage device in a state where an irreversible reaction occurs at the positive electrode due to overcharge. For the explanation of (A) and (B), see the explanation of Fig. 21.
  • FIG. 2-5 is a diagram showing the electricity storage device in a state where it has been discharged to the initial isoelectric point. Refer to the explanation of Fig. 21 for explanation of (A) and (B).
  • FIG. 2-6 is a diagram showing an electricity storage device in a completely discharged state. See the description of Figure 21 for an explanation of (A) and (B).
  • FIG. 2-7 is a diagram showing an electricity storage device in a state where an irreversible reaction occurs due to the second overcharge!
  • FIG. 2-7 For the explanation of (A) and (B), see the explanation of Fig. 21.
  • FIG. 2-8 is a diagram showing an electricity storage device that has been completely discharged after the second overcharge.
  • FIG. 2-8 For the explanation of (A) and (B), see the explanation of Fig. 21.
  • Fig. 2-9 This is a graph showing the characteristics of the electricity storage device when open charge / discharge is repeated up to the overcharge voltage up to 5 times in Example B-1.
  • Fig. 2-10 This is a graph showing the characteristics of the electricity storage device when open charge / discharge is repeated up to the overcharge voltage up to 5 times in Example B-2.
  • FIG. 2-14 is a diagram for explaining the limit charging potential and the terminal voltage of the electricity storage device during use. See the description of Figure 1 for a description of (A) and (B).
  • FIG. 3 is a graph showing the relationship between charge / discharge capacity and voltage of an electricity storage device to which the present invention is applied.
  • the negative electrode in order to be in a state where the negative electrode is reversely charged with a positive charge at the time of complete discharge (Aspect A), or at the time of complete discharge, the negative electrode is charged with a remaining negative charge without being discharged.
  • A positive charge at the time of complete discharge
  • B the state where an irreversible reaction as described later is used.
  • the electrical charging process at the positive electrode shows the adsorption process of the anion in the low voltage region and the intercalation process in the high voltage region.
  • FIG. 3 shows typical charge / discharge characteristics of the electricity storage device of the present invention.
  • Fig. 4 shows the charge / discharge characteristics of a device using activated carbon for the positive and negative electrodes as a conventional electric double layer capacitor, together with the characteristics of the device of the present invention shown in Fig. 3.
  • the horizontal axis represents the charge / discharge capacity
  • the vertical axis represents the voltage. For example, if constant current charging is performed, the horizontal axis represents the charging capacity and also corresponds to the charging time.
  • the slope of the charge capacity voltage characteristic curve changes greatly with voltage Vt as the boundary during charging. That is, the ionic salt anion is adsorbed on the positive electrode active material up to the voltage Vt, and the anion is inter-forced on the positive electrode active material at a voltage Vt or higher.
  • the voltage Vt at which the charging process changes from adsorption to intercalation is defined as the transition voltage.
  • the charge capacity is small because the amount of cation adsorbed on the positive electrode active material having a small specific surface area is small. A large slope is observed in the voltage characteristic curve. In the subsequent charging process using intercalation, a large charge with a relatively small change in voltage can be taken in.
  • the electricity storage device of the present invention is preferably used in an intercalated state as a charge / discharge region during use.
  • the force s indicates that it can be used up to 1.5V, which is lower than the transition voltage Vt during discharge. Even in this state, the intercalated anion remains, and recharging starts from here. In this case, charging starts from the transition voltage Vt or higher without going through the adsorption process.
  • the difference between the transition voltage Vt at the time of charging and the voltage that can be used in the intercalation state at the time of discharging is usually about 0.5 V due to the influence of the current and internal resistance during charging and discharging.
  • the electricity storage device of the present invention discharge is performed while maintaining a high voltage during the discharge as described above, and thus the electricity storage capacity that can be actually used is large in the voltage range required for the electronic device.
  • the energy capacity that can be extracted corresponds to the integration of the chronopotentiogram, but the device of the present invention is also characterized by a large energy capacity because it discharges at a high voltage.
  • the chronopotentiogram of charge / discharge is gentle. This indicates that the capacity to be charged is large even at a low voltage.
  • the capacity that can be used in the range of 1.5 V or less is large in this example.
  • the electricity storage device of the present invention is characterized by a large charge capacity, particularly an energy capacity, in a relatively high voltage range that is actually used.
  • the transition voltage Vt of the electricity storage device of the present invention is preferably set in consideration of the voltage used in an actual electronic device, and is usually preferably set to 1.5 V or higher.
  • the transition voltage Vt depends on the capacity of the positive electrode active material and the capacity of the negative electrode active material, particularly the ratio thereof, the transition voltage Vt can be adjusted by a combination of both. . When the capacity of the positive electrode active material is large, the transition voltage Vt is low, and when the capacity of the negative electrode active material is large, the transition voltage Vt is high.
  • the electricity storage device of the present invention for example, by adjusting the capacities of the positive electrode active material and the negative electrode active material, that is, by adjusting the transition voltage Vt, during charging (that is, interaction with the positive electrode active material).
  • the decomposition reaction of the electrolyte in the positive electrode can be suppressed, and the cycle characteristics can be improved.
  • the inventor decomposes the electrolytic solution (solvent) on the positive electrode, and the organic substance of the decomposition products accompanying this decomposition moves to the negative electrode side.
  • the starting voltage for the decomposition of the electrolyte depends on various factors, such as the type and surface area of the activated carbon, and the capacity ratio between the positive and negative electrodes. In this example of the electricity storage device of the present invention, about 3.2 V (Fig. 3), while in the conventional electric double layer capacitor, a decomposition reaction current is observed from about 2.3 V (Fig. 4), respectively! /, The
  • the capacitance ratio between the negative electrode and the positive electrode is reduced, and the transition voltage is set low. While the charging capacity increases, charging can be performed up to a range where the absolute value of the negative electrode potential is small and the increase in the positive electrode potential is small. As a result, even if the usable voltage range of the electricity storage device is widened, it can be used within a potential where the electrolyte decomposition reaction is sufficiently suppressed. As described above, charging in the positive electrode active material shows a two-stage process of adsorption and intercalation, so that the electricity storage device of aspect A can take a large discharge capacity and discharge energy. Considering the decomposition of the electrolyte during use, this electricity storage device is extremely excellent in terms of the discharge capacity and discharge energy that can be used in actual equipment and the cycle characteristics!
  • the capacitance ratio between the negative electrode and the positive electrode is increased to set the transition voltage high. While the charging capacity increases, the negative electrode power Charging is possible up to a range with a large absolute value. As a result, the resolved voltage as viewed from the device voltage increases. Therefore, in addition to the increase in the usable voltage of the electricity storage device, it can be used in a voltage range in which the electrolytic solution decomposition reaction is sufficiently suppressed. Under such conditions of use, the deposition of organic matter on the negative electrode is suppressed and the capacity reduction of the electricity storage device is improved, resulting in improved cycle characteristics. Specifically, in FIGS.
  • the charge / discharge capacity that can be used in the electricity storage device is in the range of 3.2 V to; 1.5 V, so 2.3 V to 1; It exceeds the charge / discharge capacity of electric double layer capacitors that can only be used in the 5V range. Furthermore, when compared with the discharge energy, the storage device that shows the sequential charging process is more than three times the electric double layer capacitor.
  • aspect B by showing the two-stage process of charging power adsorption and intercalation in the positive electrode active material as described above, by setting the transition voltage Vt relatively high, it is possible to An electricity storage device can increase the available discharge capacity and discharge energy. Furthermore, considering the decomposition of the electrolyte, this storage device having a transition voltage is extremely excellent in terms of discharge capacity and discharge energy that can be used in an actual apparatus, and cycle characteristics.
  • the capacity expansion in the embodiment A of the present invention is to increase the ion utilization rate of the activated carbon of the negative electrode. This mechanism will be explained with reference to Fig. 1-1 to Fig. 1-8.
  • (A) and (B) show the same charge / discharge state
  • (A) is a schematic diagram showing the relationship between the capacity and potential of positive and negative electrodes, voltage, and the horizontal axis is potential
  • the vertical axis represents the capacitance (dQ / dV).
  • (B) is a schematic diagram of the battery structure, and describes the electrons and holes held by the positive electrode and the negative electrode, and the charge balance.
  • FIG. 11 shows the electricity storage device before charging.
  • the anions and cations were not intercalated or adsorbed on the positive and negative electrodes.
  • the squares of the positive and negative electrodes are the height of the capacitance, the potential position in the horizontal position is the chargeable range, and the area of the square is the accumulated capacity of each (the integrated electric charge that can be charged by normal charging) mAH) is schematically represented.
  • the capacity of the positive electrode is the sum of the adsorption capacity and intercalation capacity.
  • FIG. 12 (B) shows the state where the positive and negative electrode capacities were partially charged.
  • FIG. 13 (B) N electrons flow in the negative electrode due to the positive force, N electrons accumulate in the negative electrode, and N holes accumulate in the positive electrode.
  • FIG. 13 (A) the accumulated capacity of the negative electrode is fully charged, but the chargeable capacity still remains in the positive electrode (“extra portion” in the figure).
  • Such a state can be achieved by setting the accumulated capacity of the positive electrode to be larger than the accumulated capacity of the negative electrode.
  • the positive electrode cumulative capacity / negative electrode cumulative capacity ratio is preferably in the range of 1.;! ⁇ 2.0.
  • the effect of this aspect is exhibited even when the integrated capacity ratio exceeds 2.0, but when the integrated capacity ratio is 2.0 or more, the amount of the positive electrode active material not involved in charge / discharge becomes excessive, and the device capacity decreases.
  • the positive electrode integrated capacity / negative electrode integrated capacity ratio is 1.2 to 1.6.
  • the positive electrode cumulative capacity / negative electrode cumulative capacity ratio can be achieved by changing the weight ratio of the positive electrode and the negative electrode together with the selection of materials (selection of a material with a large capacity per unit weight or a small material).
  • the positive electrode potential is 5.5 V vs. Li + / Li or less (preferably 5.2 V or less), and the negative electrode potential is 1.9 V vs. Li + / Li.
  • the charging voltage between both electrodes is assumed to be 3.5V.
  • Figure 15 shows the state until the charged N electrons are discharged. Despite N + n electrons flowing on the negative electrode side, the number of electrons that can be discharged is N minus the amount of reaction current. N electrons flow into the positive electrode, leaving n holes on the positive electrode.
  • Figure 16 shows the fully discharged state. Assuming that the charge quantity of the n positive holes unevenly distributed in the positive electrode in Fig. 15 is Q, in the fully discharged state (Fig. 16), Q is distributed in proportion to the positive and negative electrostatic capacities. The potential is balanced. Let Cc be the electrostatic capacity of the adsorption part of the positive electrode, Vc be the distributed voltage, Ca be the electrostatic capacity of the adsorption part of the negative electrode, and Va be the distributed voltage.
  • the square height representing the capacity of the negative electrode is actually used as a negative electrode active material, as indicated by the height of the square representing the capacity due to adsorption of the positive electrode.
  • the capacitance of activated carbon is much larger than the capacitance of the adsorption part of graphite used as the positive electrode active material.
  • the capacity of the electricity storage device is calculated as the integration of the original negative electrode schematically shown by the negative electrode square in Fig. 11 (A).
  • Qa will increase the capacity that can be charged and discharged.
  • overcharging may be performed only once, but may be performed multiple times.
  • an example of continuing the second overcharge will be described.
  • the second overcharge the same operation as in the first overcharge is performed. Charge so that the irreversible reaction start potential (in this example, reductive decomposition potential of the solvent) is exceeded on the negative electrode side so that an irreversible reaction occurs even in the second overcharge.
  • the irreversible reaction start potential in this example, reductive decomposition potential of the solvent
  • the electrolyte will begin to decompose, ie overcharge.
  • m electrons are newly consumed for decomposition of the electrolyte
  • m holes are stored in the positive electrode. In this state, the number of electrons stored in the negative electrode is N, whereas the number of holes stored in the positive electrode is N + n + m.
  • m n may be satisfied.
  • FIG. 19 is a dQ / dV curve obtained from the charge / discharge curve in the electricity storage device of this embodiment, in which open charge / discharge by overcharge is repeated 10 times (Example A-1 described later).
  • the upper curve group shows the charging process
  • (1) shows the first charge
  • (10) shows the 10th charge.
  • the lower curve group shows the discharge process. From this figure, if charging and discharging are repeated within the range where irreversible reaction occurs, the voltage at which charging by intercalation starts at the positive electrode decreases (the rising voltage of the dQ / dV curve during charging decreases) .
  • the charge capacity is the integral value of the dQ / dV curve at the time of charge, so in a storage device that has been repeatedly overcharged 10 times, the charge capacity increases! .
  • the dQ / dV curve shows a specific shape based on the specific charge / discharge mechanism.
  • Figure 1-10 shows a graph of the dQ / dV curves extracted from the 1st overcharge and 10th overcharge processes from Figure 1-9.
  • the dQ / dV increases as the voltage rises after the curve rises.
  • the dQ / dV value gradually decreased immediately after the charge voltage V increased and the canyon intercalation at the positive electrode started, and then the dQ / dV value gradually decreased (in the figure).
  • dQ / dV increases gradually again after obtaining the minimum value. Since the electricity storage device of this embodiment is manufactured through open charge / discharge at a voltage at which an irreversible reaction occurs, the above-mentioned characteristic graph shape is observed even during the charge process during normal use.
  • the dQ / dV value is inevitably lowered after the start of charging.
  • the dQ / dV curve shows a characteristic shape in which the dQ / dV value gradually decreases after showing the maximum immediately after the start of intercalation.
  • do not overcharge at a voltage that causes an irreversible reaction! / Because the storage device has no decrease in dQ / dV value during charging as shown in Figure 111, it is monotonous even after the start of intercalation. The rise continues.
  • Figure 115 shows the limit charging potential and terminal voltage during actual use (steady state).
  • the “limit potential under charge” in the figure is the limit potential at which the reductive decomposition of the solvent begins. In this example, it is 1.7 Vvs. Li + / Li.
  • the “lower limit potential” is the lower limit potential when charging on the negative electrode side.
  • Charging potential of the negative electrode is specifically 1 ⁇ 7Vvs. Li + / Li or preferably tool particularly 1 ⁇ 9Vvs. Li + / Li or favored arbitrarily.
  • the “charging upper limit potential” in the figure is the lower one of the positive electrode potential at which the oxidative decomposition reaction of the solvent starts and the negative electrode potential when the negative electrode reaches the “lower charging limit potential”. In the example shown in FIG. 115, when the negative electrode reaches the “lower limit potential”, the positive potential reaches the “upper limit potential” of 4.9 Vvs. Li + / Li.
  • charging is performed at a positive electrode potential that does not cause the oxidative decomposition reaction of the solvent at least in a range where the positive electrode potential does not exceed the “limit potential for charging”.
  • the charge potential of the positive electrode is specifically 5. 2Vvs. Li + / Li in less good Mashigusa et 4. 9Vvs. Li + / Li or less. For example 4. 6 ⁇ 5 ⁇ 2Vvs. Use to be charged in a range of Li + / Li.
  • the charging voltage (voltage between the positive and negative terminals)
  • the voltage at which the electrolyte does not decompose is 3.5 V or less, preferably 3.4 V or less, more preferably 3.2 V or less. is there.
  • the capacity of the electricity storage device can typically be increased by about 10 to 60% compared to a device that does not perform the above treatment. In a preferred example, it is increased by about 15% to 50%.
  • the transition voltage at which the charging process at the positive electrode changes from adsorption to intercalation is high, and in the asymmetric electricity storage device, when an irreversible reaction occurs at the negative electrode, In order to store the charge related to the positive electrode and make the potential the same, it is possible to store a positive charge on the negative electrode by using a part of the transition voltage.
  • the power storage device of this embodiment can use a voltage with which a voltage (transition voltage) at which anion intercalation starts is about 1.5 to 2 V, and a voltage in a low voltage region.
  • a high transition voltage indicates that the operating voltage of the device of this mode is high and high energy. In this mode, the capacity is further increased by using a voltage section up to a lower voltage range. It is intended.
  • the operating voltage range of the negative electrode expanded according to this embodiment is preferably 10% or more of the operating voltage range based on the adsorption inherent in the negative electrode, more preferably 15% or more.
  • the energy increases by about 10 to 30%.
  • the transition voltage at which intercalation starts will decrease too much, so the transition voltage should be set to 1.5 V or higher, preferably 1.7 V or higher. Is preferred.
  • the operating voltage range of the expanding negative electrode is preferably 60% or less, more preferably 50% or less.
  • the case where the irreversible reaction occurs by reductive decomposition of the solvent is exemplified.
  • the reaction is not limited to the reductive decomposition of the solvent, and a reaction in which the irreversible reaction occurs at the negative electrode by overcharge can be used. In other words, any reaction that consumes electrons at the negative electrode without adversely affecting battery performance is acceptable.
  • the voltage for overcharging is appropriately determined depending on the voltage at which irreversible reaction occurs.
  • the decomposition voltage differs depending on the solvent, so it is preferable to determine it depending on the solvent components contained in the electrolyte.
  • overcharging for causing an irreversible reaction is divided into a plurality of times, it is possible to select milder conditions than in the case of obtaining a necessary capacity increase by one overcharging. Therefore, it is generally 2 times or more, preferably 5 times or more. Further, the number of times is not particularly limited, but it is preferably about 50 times or less for work.
  • Overcharging and discharging as described above are preferably performed in an open state before the device is completed as a product. Through these processes, the product electricity storage device is completed.
  • the electricity storage device of this aspect can be charged and discharged with high capacity, it is possible to store high energy. It can be used for backup power sources for personal computers, mobile phones, mobile mopile devices, and power sources for digital cameras.
  • the power storage device of this mode can also be applied to electric vehicles and HEV power systems.
  • the discharge voltage of the electricity storage device is preferably 1.5 V or higher, and more preferably 2 V or higher.
  • the power storage device of this aspect is combined with a known voltage control means that shuts down when the voltage decreases to a predetermined voltage so that only the charge / discharge power s intercalation region is present.
  • a known voltage control means that shuts down when the voltage decreases to a predetermined voltage so that only the charge / discharge power s intercalation region is present.
  • a system is also preferable.
  • the power storage device of this aspect is a known voltage control so that the terminal voltage is limited to a predetermined voltage range so that the positive electrode potential and the negative electrode potential are in the above-described range during charging in use. It is also preferable to combine the means into a power storage system.
  • the electricity storage device of the present aspect B further improves the electricity storage device having the above-described transition voltage, increases the transition voltage, and enables use at a higher voltage. Since the anion force force is a chemical reaction, the intercalation potential cannot be changed. Increasing the transition voltage means lowering the negative electrode potential at the start of positive electrode intercalation. In this embodiment B, since the negative electrode is charged with the remaining negative charge without being discharged, the potential of the negative electrode is lowered. Therefore, even when operated at a high voltage, the positive electrode does not reach the oxidative decomposition potential of the electrolytic solution, so that the cycle characteristics are improved.
  • a high transition voltage is preferred for a high voltage storage device 1. 75 V or more, preferably 2 V or more, more preferably 2.2 V or more.
  • the cycle characteristics are deteriorated due to excessive intercalation.
  • the anion intercalation with respect to the positive electrode in the low voltage range that is not practically used. Since the Chillon load can be reduced, the cycle characteristics by this mechanism can also be improved.
  • the active material of the positive electrode of this embodiment B a graphite material capable of intercalation of anion is typically used, and as the active material of the negative electrode, a cation can be adsorbed typically. Activated carbon is used. Expressing the intercalation capacity of the positive electrode as an electrostatic capacity, the electrostatic capacity of the positive electrode graphite is about 5 to 15 times that of activated carbon.
  • the electricity storage device of this embodiment B is a conventional electric double layer using activated carbon as an active material. Compared to capacitors, it is much higher! / And has a storage capacity.
  • the discharge capacity of this electricity storage device is determined by the amount of adsorption of the cations polarized on the negative electrode on the activated carbon and the amount of anion intercalated into the graphite.
  • the amount of anion to be intercalated is the same amount of electricity as the negatively polarized cation, it can be said that the device capacity is determined by the capacity of the negative electrode that polarizes the electrolyte. Therefore, activated carbon having the highest capacity should be selected for the electricity storage device of this embodiment B.
  • FIG. 1 The mechanism for increasing the voltage in Mode B will be described with reference to Figs. 2-1 to 2-8.
  • (A) and (B) show the same state
  • (A) is a schematic diagram showing the relationship between the capacity and potential of positive and negative electrodes, voltage
  • the horizontal axis is the potential
  • the vertical axis represents the capacitance (dQ / dV).
  • (B) is a schematic diagram of the battery structure, and explains the electrons and holes held by the positive electrode and the negative electrode, and the charge balance.
  • oxidative decomposition of the solvent is taken as an example.
  • the oxidation potential of the solvent is on the high potential side and the reduction potential of the solvent is on the low potential side.
  • Fig. 2-1 shows the electricity storage device before charging.
  • the anions and cations were not intercalated or adsorbed on the positive and negative electrodes.
  • the squares of the positive and negative electrodes are the height of the capacitance, the potential range in the horizontal position is charged, and the area of the square is the integrated capacity of each (integrated electric charge that can be charged by normal charging).
  • the quantity mAH) is schematically represented.
  • the positive electrode capacity is the adsorption capacity. And the sum of the two intercalation capacities.
  • FIG. 2 (B) shows the state where the positive and negative electrode capacities were partially charged.
  • N electrons flow to the negative electrode, and the negative electrode accumulates N electrons and adsorbs N charged cations to the positive electrode.
  • N holes accumulate, anions with N charges intercalate! /.
  • the accumulated capacity of the positive electrode is fully charged, but there is still a chargeable capacity remaining on the negative electrode! Part ").
  • Such a state can be achieved by setting the accumulated capacity of the negative electrode to be larger than the accumulated capacity of the positive electrode.
  • a preferable range of the positive electrode capacity / negative electrode capacity ratio is 0.5 to 0.95. Even if the capacity ratio is less than 0.5, the effect of the present embodiment B is exhibited, but if the number of the negative electrode is excessive, the capacity reduction is increased, so 0.5 or more is preferable. When the capacitance ratio is 0.95 or more, the transition voltage shift tends to be insufficient in terms of the effect of higher voltage. A more preferable positive electrode capacity / negative electrode capacity ratio is 0.75-0.9.
  • the positive electrode potential is 5.2 V vs. Li + / Li or more (preferably 5.5 V or more) and the negative electrode potential is 1.9 V vs. Li + / Li or more, depending on the solvent system used.
  • the voltage between the two electrodes By setting the voltage between the two electrodes to 3.4 V, preferably 3.5 V or more, an irreversible decomposition reaction of the electrolyte occurs on the surface of the positive electrode. Therefore, as shown in Fig. 2-4, if the charging voltage between the two electrodes is set to 3.5 V, the battery device of this mode B, which is designed to have a negative electrode capacity larger than the positive electrode capacity, is overcharged and the electrolyte solution at the positive electrode. Oxidative decomposition occurs, and n holes are consumed at the positive electrode (n electrons are absorbed). At this time, equivalent n electrons are stored in the negative electrode.
  • Figure 2-5 shows a state where N charged electrons are discharged. N electrons flow into the positive electrode, and the positive electrode is electrically neutral and has no charge. n electrons are stored. However, in this state, the potential of the positive electrode is still slightly high, and the potentials of the positive electrode and the negative electrode are not balanced.
  • the capacity of the negative electrode is set to be sufficiently larger than that of the positive electrode, so that the decrease in capacity does not affect the capacity of the entire battery.
  • the equipotential point shifts to the lower potential side by Va. Therefore, when charging is performed, charging starts from a low potential by Va from the beginning, so that the positive intercalation start voltage (transition voltage Vt) increases by Va. Therefore, the electricity storage device of this aspect B can be charged and discharged at a high voltage.
  • overcharging may be performed only once, but may be performed a plurality of times.
  • an example of the second overcharge will be described.
  • the second charge the same operation as the first charge is performed.
  • the irreversible reaction initiation potential on the positive electrode side (in this example, the oxidation of the solvent) Charge to exceed the decomposition potential.
  • the electrolyte will be decomposed, that is, overcharge will begin.
  • m positive holes are newly consumed for the decomposition of the electrolyte at the positive electrode (absorption of m electrons)
  • m electrons are stored at the negative electrode.
  • there are N holes accumulated in the positive electrode whereas N + n + m electrons are accumulated in the negative electrode.
  • m n may be satisfied.
  • the transition voltage at which the electrical process changes from adsorption to intercalation changes to the high voltage side by Va + Va.
  • the “lower charging potential” in the figure is the higher of the negative electrode potential at which the reductive decomposition of the solvent begins or the negative electrode potential when the positive electrode reaches the “upper charging limit potential”.
  • 1.7 Vvs. Li + / Li is shown as an example where they are exactly equal.
  • Negative electrode charging The electric potential is preferably 1.7 Vvs. Li + / Li or more, particularly preferably 1 ⁇ 9 Vvs. Li + / Li or more.
  • the charging voltage (voltage between the positive and negative terminals)
  • the voltage at which the electrolyte does not decompose is 3.5 V or less, preferably 3.4 V or less, more preferably 3.2 V or less. is there.
  • the transition voltage of the electricity storage device increases by about 0.5V, or 1.5V.
  • an electrical storage device having a high transition voltage can be obtained by performing one or more open charge / discharge cycles at a voltage at which an irreversible reaction occurs on the positive electrode side.
  • a high transition voltage means that the operating voltage of the device is high and high energy.
  • the force by which the negative electrode capacity is gradually reduced by the treatment of the present embodiment B This decrease in capacity is a decrease in capacity in a low voltage operation region of 2 V to 2.2 V or less in the storage device of the present embodiment B. Therefore, there is no change in the capacity in the practical high voltage range. In other words, when charging / discharging in the low voltage range from 0V to 1.75V to 2V, the capacity appears to decrease in capacity.
  • a material that decomposes at the positive electrode during overcharge may be added in advance.
  • the electric capacity that decomposes at the positive electrode during open charge can be stored at the negative electrode, and the transition voltage can be increased by the potential corresponding to the charge. This method is effective in improving cycle characteristics because no excessive anion intercalation is performed on the positive electrode.
  • the voltage for overcharging is appropriately determined depending on the voltage at which the irreversible reaction occurs.
  • the decomposition voltage differs depending on the solvent, so it is preferable to determine it depending on the solvent component contained in the electrolyte.
  • the overcharge for causing the irreversible reaction is divided into multiple times, it is possible to select milder conditions than when obtaining the required capacity increase with a single overcharge. Therefore, it is generally 2 times or more, preferably 5 times or more. Further, the number of times is not particularly limited, but it is preferably about 50 times or less for work.
  • the overcharge and discharge as described above are preferably performed in an open state before the device is completed as a product. Through these processes, the product electricity storage device is completed.
  • the electricity storage device of the present aspect B operates even at a high voltage of 3 V or more, and can be charged and discharged with a high capacity, and thus can store high energy. Its use can be used for PC backup power supplies, mobile phones, portable mopile devices, and digital camera power supplies. In addition, the electricity storage device of aspect B can also be applied to electric vehicles and HEV power systems.
  • the power storage device according to the present aspect B is combined with a known voltage control unit that shuts down when the voltage decreases to a predetermined voltage so that charging / discharging is performed only in the intercalation region.
  • a known voltage control unit that shuts down when the voltage decreases to a predetermined voltage so that charging / discharging is performed only in the intercalation region.
  • a system is also preferable.
  • the electricity storage device of the present aspect B is publicly known to limit the inter-terminal voltage to a predetermined voltage range so that the positive electrode potential and the negative electrode potential are in the above-mentioned range during charging during use. It is also preferable to combine with other voltage control means to make a power storage system! /.
  • the electricity storage device of the present invention materials such as a positive electrode active material, a negative electrode active material, a binder, a conductive material, a current collector, a separator, and an electrolytic solution are used.
  • materials such as a positive electrode active material, a negative electrode active material, a binder, a conductive material, a current collector, a separator, and an electrolytic solution are used.
  • Examples of the shape of the electricity storage device include a winding type, a stack type, and a twist.
  • any conventional technology such as EcaSS (trademark) can be suitably used as a system for extracting electric capacity.
  • graphite means a hexagonal network plane with SP2 hybrid orbital carbon atoms, and this two-dimensional lattice structure is regularly stacked as a basic structural unit (crystallite). Good thing, has strong anisotropy.
  • Graphite material means that graphite is sufficiently generated. In the present application, black lead is included.
  • a carbon material is used as an active material for both the positive electrode and the negative electrode.
  • the active material for the positive electrode include graphite materials.
  • the graphite material used as the positive electrode active material may be either natural graphite or artificial graphite. When obtaining a higher capacity, it is preferable to use highly crystalline graphite. In order to achieve good intercalation, the interlayer distance of the graphite material is preferably 0.3357 nm or less, more preferably 0.3355 nm or less.
  • the crystal structure of graphite material includes hexagonal structure ( ⁇ ⁇ stacking period) and rhombohedral structure (ABCABC “stacking period).
  • rhombohedral structure is introduced by grinding.
  • graphite having no rhombohedral structure is preferable.
  • the outer surface area of the graphite material particles is preferably larger, that is, the more preferable (that is, the smaller the graphite particles, the more preferable it is).
  • the rhombohedral structure is often introduced, and the crystallinity of the graphite material is often impaired. Therefore, the average particle diameter of the preferable black lead material is 3 to 40 m, and more preferably 6 to 25 m.
  • the specific surface area of the graphite material for example, when a rhombohedral structure is not introduced using a jet mill or the like, and the powder is pulverized while maintaining the crystallinity of the graphite material, the specific surface area; ! ⁇ 20m 2 / g can be adjusted to S, 10m 2 / g or less, more preferably 2 to 5m 2 / g in order to lower the decomposition rate of the solvent on the positive electrode surface. preferable.
  • the tap density of the consolidated graphite is 0 ⁇ 8 ⁇ ;! ⁇ 4 g / cc, and the true density is 2.2 ⁇ 22 g / cc or more.
  • the ratio of the graphite material of 1 ⁇ m or less is substantially 10% or less, the decrease in the bulk density of the graphite is suppressed and the increase in the surface area is also suppressed.
  • the carbon-based material used as the negative electrode active material it is preferable to select a material that only adsorbs ions during charging and discharging, that is, a material that does not generate intercalation. Quality materials. Material with a larger specific surface area than the active material of the positive electrode Is preferred. When using a graphite material, a material different from the material of the active material of the positive electrode is preferred, and a material having a specific surface area larger than that of the graphite material used for the positive electrode is selected. As the activated carbon, known activated carbon for capacitors can be used.
  • chemical activated coconut shell activated carbon for example, chemical activated coconut shell activated carbon, steam activated coconut shell activated carbon, phenol resin activated carbon and pitch activated carbon, or alkali activated phenol resin activated carbon and mesophase pitch activated carbon can be used.
  • high surface area black lead material for example, high surface area black lead material, CVD-treated activated carbon or graphite material can also be used.
  • Carbonaceous material used as the active material of the negative electrode the specific surface area is 300 meters 2 / g or more preferably has a high surface area of good Mashigu particularly 450m 2 / g ⁇ 2000m 2 / g. Normally, it is preferable to use activated carbon as the negative electrode active material, but when high density storage capacity per volume is desired, high surface area graphite material can be compacted to increase bulk density, which is preferable. It is.
  • the binder is not particularly limited, and PVDF, PTFE, polyethylene, rubber-based binders, and the like can be used.
  • rubber-based binder components include rubbers typified by aliphatics such as EPT, EPDM, butyl rubber, propylene rubber and natural rubber, or rubbers containing aromatic rubbers such as styrene butadiene rubber. It is done.
  • the structure of these rubbers may contain a hetero-containing substrate such as nitrile, acrylic, force sulfonyl, or silicon, and is not limited to straight chain or branching. In addition, even if these are used individually or in mixture of several, it can become a favorable binder.
  • a conductive material such as carbon black or ketjen black may be added.
  • pure aluminum foil is generally used. Pure aluminum foil or aluminum containing a single metal or a plurality of metals such as copper, manganese, silicon, magnesium, and zinc may be used. Also, stainless steel, nickel cane, titanium, etc. are used similarly. In addition, in order to increase conductivity and secure strength, those added with the above mixture and other elements can also be used. At this time, the surface of these substrates may be roughened by etching or the like, or a conductive metal or carbon may be embedded in the substrate, or may be coated. These current collectors are foil But it can also be used in mesh form.
  • separator in addition to cellulose paper and glass fiber paper, polyethylene terephthalate, polyethylene, polypropylene, polyimide microporous film and a multilayer film composed of these layers are used. Alternatively, PVDF, silicon resin, rubber resin, etc. can be coated on the surface of these separators, or metal oxide particles such as aluminum oxide, silicon dioxide, and magnesium oxide may be embedded. . Of course, these separators may be used by arbitrarily selecting two or more types of separators that do not matter even if there is one or more between the positive and negative electrodes.
  • Organic solvents used as the electrolyte include cyclic carbonates such as propylene carbonate, cyclic esters such as ⁇ -petit-lataton, ⁇ ⁇ heterocyclic compounds such as methylpyrrolidone, nitriles such as acetonitrile, and other sulfolanes and sulfoxides.
  • Polar solvent can be used.
  • solvents can be used alone or in combination of two or more.
  • ammonium salts such as ammonium salt, pyridinium salt, pyrrolidinium salt, piperidinium salt, imidazolium salt, and phosphonium salt are preferred as anions of these salts.
  • Fluorine compounds such as phosphate ion (PF-) and trifluoromethanesulfonate ion are preferred.
  • Jetyldimethylammonium fluoride triethylmethylammonium borofluoride, Hof Butylmethyl ammonium, borofluoride tetrabutyl ammonium, borofluoride tetrahexyl ammonium, borofluoride propyltrimethylammonium, borofluoride butyltrimethylammonium, borofluoride heptyltrimethylammonium, borofluoride (4 pentyl) trimethylammonium, tetradecyltrimethylammonium borofluoride, hexadecyltrimethylammonium borofluoride, heptadecyltrimethylammonium borofluoride, octadecyltrimethylammonium borofluoride, 1,1, -difluoro-2,2-bipyridinium bistetrafluoroborate, borofluoride N, N di
  • electrolytes can be used alone or in combination of two or more.
  • TIMCAL Ltd. Graphite Tim Rex KS6 as a positive electrode active material (002 interlayer distance 0. 3357 ⁇ m, an average particle diameter of 3.4 111, surface area of 20 m 2 / g) Powder electrochemical Co. acetylene Bed rack 8 parts per 84 parts After mixing, a slurry was prepared with an NMP solution of 8 parts of PVDF manufactured by Kureha Chemical Co., Ltd., and an electrode having a thickness of 140 m was prepared on an aluminum foil. As a negative electrode active material, Kuraray Chemical Co., Ltd.
  • activated carbon RP-20, average particle size 2 111, surface area 1800m 2 / g 84 parts of acetylene black is mixed with powder, then PVDF 8 parts NMP solution to prepare slurry, A negative electrode having a thickness of 100 Hm was prepared on an aluminum foil.
  • the weight ratio of positive electrode active material weight / negative electrode active material weight was 1.25 / 1, glass fiber was used for the separator, and 1.5 M / liter TEMABF PC solution was used for the electrolyte, and the electrode area was 3. 14 cm 2
  • Assembling type cell was assembled.
  • the gas generated in this cell is a gap in the Teflon insulation sleeve. Is released.
  • CC charge constant current charge
  • CV charge constant voltage charge
  • the discharge capacity when CC discharge to 0 V at 1 mA was 37.6 mAh / g (based on the weight of the positive electrode active material).
  • CC charging was performed up to 3.5V as an open charge, and CV charging was performed at 3.5V for 10 minutes. After that, 10 cycles of CC discharge to 0V at 1mA were performed.
  • Fig. 19 shows a dQ / dV curve obtained by converting the charge / discharge curve up to 10 cycles at the time of open charge based on the voltage change. From Fig. 19, it can be seen that the capacity increases with each cycle and the transition voltage decreases. 3.
  • the charge voltage was changed to 3.2V and a charge / discharge test was conducted. 3.
  • the discharge capacity after 2V charge was 48.4 mAh / g (based on the weight of the positive electrode active material), and the capacity increased by 28.7% by the open charge treatment of this embodiment.
  • Activated carbon RP-20 (Kuraray Chemical Co., Ltd.) with a mean particle size of 2 m and a surface area of 1800 m 2 / g as a positive and negative electrode active material.
  • a positive electrode having a thickness of 150 am and a negative electrode having a thickness of 100 ⁇ m were prepared on an anoremi foil.
  • the weight ratio of positive electrode active material weight / negative electrode active material weight was adjusted to 1.5 / 1, and an assembly type cell was assembled in the same manner as in Example A-1. CC charge to 2.3V at 1mA and CV charge at 2.3V for 10 minutes.
  • the initial discharge capacity after CC discharge to 1 V at 0 mA was 25.8 mAh / g (based on the weight of the positive electrode active material), and the same as Example A-1 except that the voltage was 2.6 V. 10 Cycle open charge.
  • CC charge to 2.3V was performed again at 1mA, and CV charge was performed at 2.3V for 10 minutes.
  • the discharge capacity after CC discharge to 0V at 1mA was 23. OmAh / g (based on the weight of positive electrode active material), and no increase in capacity due to open charge was observed.
  • Graphite Timrex SFG44 manufactured by TIMCAL as positive electrode active material (002 interlayer distance 0.335 4 nm, average particle diameter 23.8 m, surface area 5 m 2 / g) 8 parts of acetylene black manufactured by Electrochemical Co., Ltd. as powder
  • a slurry was prepared with an NMP solution of 8 parts of PVDF manufactured by Kureha Chemical Co., Ltd., and an electrode having a thickness of 140 m was prepared on an aluminum foil.
  • Kuraray Chemical as negative electrode active material After mixing 8 parts of acetylene black with 84 parts of activated carbon RP-20, average particle size 2 111, surface area 1800m 2 / g, a slurry was prepared with NMP solution of 8 parts of PVDF, and the thickness on the aluminum foil A 100 am negative electrode was prepared.
  • the weight ratio of positive electrode active material weight / negative electrode active material weight is 1.2 / 1, glass fiber is used for the separator, and 1.5 M / liter TEMABF PC solution is used for the electrolyte, and the electrode area is 3. 14 cm 2
  • Assembling type cell was assembled. The gas generated in this cell is released from the gap between the Teflon insulation sleeves. In the 1st and 2nd cycles, CC charge was performed at 1mA to 3.2V, and 3.2V was charged for 10 minutes. After that, CC was discharged to 0V at 1mA. The discharge capacity in the second cycle was 41.6 mAh / g (based on the weight of the positive electrode active material).
  • TIMCAL graphite Timrex SFG44 (002 interlayer distance 0.335 nm, average particle diameter 23.8 m, surface area 5.
  • Om 2 / g) 84 parts by Electrochemical Acetylene Black 8 parts
  • slurry was prepared with NMP solution of 8 parts PVDF manufactured by Kureha Chemical Co., Ltd., and an electrode was prepared on aluminum foil.
  • 8 parts of acetylene black was mixed with 84 parts of activated carbon RP-20, Kuraray Chemical Co., Ltd., average particle size 2 111, surface area 1800 m 2 / g, and then a slurry was prepared with 8 parts of PVDF NMP solution.
  • a negative electrode was prepared on an aluminum foil.
  • the weight ratio of positive electrode active material weight / negative electrode active material weight is 1 / 1.5, glass fiber is used for the separator, 1.5M / Litt Nore PC solution of TEMABF is used for the electrolyte, and the electrode area is 3. 14cm.
  • Two assembled cells were assembled. The generated gas is released from the gap between the Teflon insulation sleeves. First, CC charge (constant current charge) was performed up to 3.5V at 1mA, and CV charge (constant voltage charge) was performed at 3.5V for 30 minutes. Thereafter, 5 cycles of CC discharge to 1 V at 1 mA and CV discharge at 0 V for 30 minutes were performed.
  • Figure 2-9 shows the dQ / dV curve obtained by converting the charge / discharge curve at this time based on the voltage change. From this figure, it can be seen that the transition voltage increases with each site. On the other hand, the discharge capacity at high voltage was almost constant despite the high transition voltage.
  • a positive electrode and a negative electrode were prepared in the same manner as in Example B-1, and an assembly type cell was prepared.
  • TIMCAL graphite Timrex SFG15 (002 interlayer distance 0.33 55 nm, average particle size 8.8 m, surface area 9.5 m 2 / g) is used for the positive electrode graphite
  • the graphite porous body SP440 (002 interlayer distance 0. 3371nm, the average particle diameter of 13. O ⁇ m, surface area 440m 2 / g) was used.
  • the positive electrode / negative electrode weight ratio was 1/2. Using this cell, CC charge was first performed to 3.5V at 1mA, and CV charge was performed at 3.5V for 30 minutes.
  • Figure 2-10 shows the dQ / dV curve obtained by converting the charge / discharge curve at this time based on the voltage change.
  • a positive electrode and a negative electrode were prepared by the method of Example B-1. However, the weight ratio of the positive electrode active material weight / negative electrode active material weight was adjusted to 1/1.
  • An assembly type cell was assembled in the same manner as in Example B-1. CC charge to 3.2V at 1mA and CV charge at 3.2V for 30 minutes. afterwards 5 cycles of CC discharge to OV at 1 mA and CV discharge for 30 minutes at OV. There was no significant change in transition voltage after 5 cycles. The results are shown in Figure 2-11. 3.
  • the discharge capacity in the 10th cycle of 2V charge was 46.5 mAh / g (positive electrode weight basis) in the voltage range of 1.4V to 3.2V.
  • the voltage at the time of discharge extended to a low voltage, which was slightly inferior in terms of energy capacity.
  • a 2032 coin cell was prepared with the same electrode configuration prepared in Example B-1 and Comparative Example B-1, and a cycle test was performed 5000 times at a 10C rate between 2.3V and 3.2V.

Landscapes

  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un dispositif de charge comportant une anode contenant une substance d'activation carbonique et une cathode. Un procédé de charge électrique sur l'anode indique un procédé d'adsorption d'anions dans une zone à basse tension et un procédé d'intercalation dans une zone à haute tension. La charge électrique sur la cathode est provoquée par l'adsorption de cations. Au moment de la décharge complète, l'état est rendu tel que la cathode est chargée de manière inverse avec la charge positive, ou tel que la cathode est chargée avec la charge négative non libérée mais conservée.
PCT/JP2007/069315 2006-10-03 2007-10-02 DISPOSITIF DE charge ET Son procÉDÉ DE FABRICATION Ceased WO2008041714A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2006-272318 2006-10-03
JP2006272318A JP4863001B2 (ja) 2006-10-03 2006-10-03 蓄電デバイスおよびその製造方法
JP2006272317A JP4863000B2 (ja) 2006-10-03 2006-10-03 蓄電デバイスおよびその製造方法
JP2006-272317 2006-10-03

Publications (1)

Publication Number Publication Date
WO2008041714A1 true WO2008041714A1 (fr) 2008-04-10

Family

ID=39268568

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/069315 Ceased WO2008041714A1 (fr) 2006-10-03 2007-10-02 DISPOSITIF DE charge ET Son procÉDÉ DE FABRICATION

Country Status (1)

Country Link
WO (1) WO2008041714A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3355329A4 (fr) * 2015-12-16 2019-03-27 Shanghai Aowei Technology Development Co., Ltd. Condensateur au lithium-ion et son procédé de formation
WO2022107892A1 (fr) * 2020-11-20 2022-05-27 株式会社村田製作所 Batterie secondaire, système de commande de batterie secondaire, et bloc-batterie
CN116825552A (zh) * 2023-06-20 2023-09-29 浙江大学 一种适用于超低温的超级电容器用电解液、超级电容器

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0757978A (ja) * 1993-08-18 1995-03-03 Okamura Kenkyusho:Kk 電気二重層コンデンサの充電方法
JPH08107047A (ja) * 1994-10-04 1996-04-23 Petoca:Kk 電気二重層キャパシタ
JPH11307404A (ja) * 1998-04-24 1999-11-05 Isuzu Advanced Engineering Center Ltd 電気二重層キャパシタ及び正極用活性炭並びに電気二重層キャパシタの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0757978A (ja) * 1993-08-18 1995-03-03 Okamura Kenkyusho:Kk 電気二重層コンデンサの充電方法
JPH08107047A (ja) * 1994-10-04 1996-04-23 Petoca:Kk 電気二重層キャパシタ
JPH11307404A (ja) * 1998-04-24 1999-11-05 Isuzu Advanced Engineering Center Ltd 電気二重層キャパシタ及び正極用活性炭並びに電気二重層キャパシタの製造方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3355329A4 (fr) * 2015-12-16 2019-03-27 Shanghai Aowei Technology Development Co., Ltd. Condensateur au lithium-ion et son procédé de formation
WO2022107892A1 (fr) * 2020-11-20 2022-05-27 株式会社村田製作所 Batterie secondaire, système de commande de batterie secondaire, et bloc-batterie
JP7464146B2 (ja) 2020-11-20 2024-04-09 株式会社村田製作所 二次電池、二次電池制御システムおよび電池パック
CN116825552A (zh) * 2023-06-20 2023-09-29 浙江大学 一种适用于超低温的超级电容器用电解液、超级电容器

Similar Documents

Publication Publication Date Title
JP4888667B2 (ja) 蓄電デバイスおよび蓄電システム
JP4731967B2 (ja) リチウムイオンキャパシタ
Rauhala et al. Lithium-ion capacitors using carbide-derived carbon as the positive electrode–A comparison of cells with graphite and Li4Ti5O12 as the negative electrode
US7848081B2 (en) Lithium-ion capacitor
US8792224B2 (en) Hybrid capacitor
JP4918418B2 (ja) リチウムイオンのプレドープ方法およびリチウムイオン・キャパシタ蓄電素子の製造方法
KR100570359B1 (ko) 하이브리드 전지
CN103201805B (zh) 锂离子电容器
WO2016209460A2 (fr) Pseudocondensateurs hybrides à haute densité d'énergie et procédé de leur fabrication et utilisation
JP6284198B2 (ja) 蓄電デバイスの製造方法
AU2188099A (en) Non-aqueous electrolyte for electrochemical systems and lithium secondary battery comprising the same
JP2008252013A (ja) リチウムイオンキャパシタ
JP2014207453A (ja) 蓄電デバイス
WO2008041714A1 (fr) DISPOSITIF DE charge ET Son procÉDÉ DE FABRICATION
KR100537366B1 (ko) 하이브리드 캐패시터
JP4863000B2 (ja) 蓄電デバイスおよびその製造方法
JP4863001B2 (ja) 蓄電デバイスおよびその製造方法
JP2012089823A (ja) リチウムイオンキャパシタ及びその製造方法
WO2023117492A2 (fr) Compositions de matériau d'électrode pour électrodes d'accumulateurs d'énergie présentant des capacités de charge et de décharge rapides
EP1816661A1 (fr) Condensateur electrique a couche double
EP4475225B1 (fr) Cellules de stockage d'énergie à capacités de charge et de décharge rapides
JP2007294539A (ja) リチウムイオンハイブリッドキャパシタ
EP4481779A1 (fr) Compositions d'électrolyte pour cellules de stockage d'énergie à charge rapide et capacités de décharge
JP2008034304A (ja) エネルギー貯蔵デバイス
JP2009026508A (ja) 蓄電デバイス

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: 07829055

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07829055

Country of ref document: EP

Kind code of ref document: A1