WO2022191202A1 - Positive electrode and storage battery - Google Patents

Positive electrode and storage battery Download PDF

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WO2022191202A1
WO2022191202A1 PCT/JP2022/010075 JP2022010075W WO2022191202A1 WO 2022191202 A1 WO2022191202 A1 WO 2022191202A1 JP 2022010075 W JP2022010075 W JP 2022010075W WO 2022191202 A1 WO2022191202 A1 WO 2022191202A1
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positive
electrode active
lithium
reaction
positive electrode
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PCT/JP2022/010075
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French (fr)
Japanese (ja)
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茂 佐野
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茂 佐野
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Priority to CN202280019865.5A priority Critical patent/CN116941065A/en
Publication of WO2022191202A1 publication Critical patent/WO2022191202A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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 positive electrode active material for storage batteries. Moreover, it is related with the storage battery comprised by the positive electrode active material.
  • the lithium-ion storage battery which was commercialized by Sony Corporation in 1991, has a high energy density and is widely used in laptop computers, mobile phones, etc. Recently, it has been in the limelight as a battery for electric vehicles.
  • gasoline cars can run more than 1000km with a full tank of gasoline, but the mileage of one charge of the Nissan Leaf, an electric car currently on the market, is 400km in the catalog value. Insufficient distance. Therefore, it is desired to develop an innovative battery that can run 1000km on one charge, that is, has more than twice the energy density.
  • the pores of the positive and negative electrode active materials which have a porous structure, are drawn in a cylindrical shape as shown in FIG.
  • the surfaces of both electrodes are covered by an SEI (solid electrolyte interface) formed by reaction with the electrolyte or a "sieve membrane” that allows the passage of charge carrier ions such as lithium ions but blocks the passage of solvents such as ethylene carbonate. , and there is no solvent in the pores.
  • Electrons are injected into the negative electrode active material by charging, and electron deficiencies are injected into the positive electrode active material. Negative ions are stored and charged in the pores.
  • the reaction formula is as follows.
  • lithium metal can be used as the negative electrode and graphite, which is the current negative electrode, can be discharged as the positive electrode is well known and put into practical use as a technique called "pre-doping" in which lithium ions are inserted in advance for SEI formation processing of the carbon electrode.
  • pre-doping a technique called "pre-doping” in which lithium ions are inserted in advance for SEI formation processing of the carbon electrode.
  • This reaction is reversible, and a lithium metal deposition reaction occurs at the negative electrode, and a lithium ion insertion/extraction reaction occurs at the positive electrode.
  • the reaction formula is as follows.
  • the positive electrode can be charged to a state where lithium ions are not inserted, and can be discharged to an intermediate state.
  • the theoretical capacity of current graphite is 372 mAh.
  • the capacity is about three times that of graphite, or 1000 mAh, and the capacity per volume is about two times, or 700 mAh.
  • the potential difference between the positive and negative electrodes, that is, the storage battery voltage is only about half that of the current lithium ion storage battery, and the energy density cannot be improved.
  • Figure 4 was drawn with reference to Non-Patent Document 4.
  • lithium ions move from the positive electrode lithium cobaltate to the negative electrode current collector Pt in the solid electrolyte LATSPO.
  • An existing distribution area can be created.
  • the concentration changes continuously and the concentration gradient becomes like an exponential function. It was named "in-situ formation negative electrode” because lithium ions in the region of 700 nm distributed in high concentration increase and decrease with charging and discharging.
  • the left diagram of FIG. 5 is a state diagram showing nano-sized voids, crevices, and cracks formed in the solid electrolyte due to strain in the crystal due to the insertion of lithium ions during the initial charge. According to the presenter's explanation, the presence of voids can be observed by observation with a transmission microscope after charging and discharging, but the existence of lithium ions in the voids cannot be measured due to insufficient measurement resolution. .
  • Lithium ions are charged and discharged by inserting/deintercalating them into and out of the voids.
  • the "cantilever theory" demonstrated by computational chemistry described in Non-Patent Documents 1, 2 and 3 is not limited to carbon nanotubes, but qualitatively To establish.
  • the right view of FIG. 5 is an enlarged view of the void, and lithium ions are arranged at regular intervals along the wall of the void. They are not sandwiched in the center of the gap, nor are they clustered together.
  • the intercalation of lithium ions during the initial charge causes strain in the crystal, forming voids.
  • the carbon nanotubes in Non-Patent Documents 1 and 2 are replaced by solid electrolytes exhibiting "voids" and electronic conductivity.
  • the reaction formula is as follows.
  • Negative charge (formation) reaction Li + + ⁇ void> + e - ⁇ ⁇ void Li + e - >
  • the positive and negative electrodes are determined by which side has the higher potential, so in the case of a reversible reaction, depending on the partner, it can be either the positive electrode or the negative electrode.
  • the "in-situ negative electrode” also becomes an "in-situ positive electrode” if the mating electrode is metallic lithium.
  • the stored energy of a lithium-ion secondary battery is the product of the amount of stored electricity and the voltage.
  • Conventional theory and technology can be used to increase the capacity, but there was no theory or technology that could obtain a voltage of 3.6 V, which is equivalent to that of current lithium-ion batteries, using the same materials.
  • n Divide the positive electrode into n elements. Since the n divisions are made virtually, they do not have to be in a specific place, they do not have to be even, they may be arbitrary, and the number of n may be arbitrary or infinite.
  • the electrical characteristics of each n part can be written as follows.
  • n part equilibrium potential ⁇ ⁇ (electronic resistance + ion transfer resistance) of n part ⁇ * ⁇ current of n part ⁇ ⁇ charge transfer overvoltage of n part ⁇ SOC adjustment of n part active material heterogeneity Since the n parts obtained by dividing the reaction surface ion concentration correction voltage of ⁇ n parts are connected in parallel, the charging/discharging (closed circuit) potentials of the n parts with respect to the negative electrode are all the same from 1 to n.
  • the electronic resistance of the n part, the ion transfer resistance of the n part, the charge transfer overvoltage of the n part, the SOC adjustment voltage of the active material non-uniformity of the n part, and the reaction surface ion concentration correction voltage of the n part are all different in the n part, Since the current in the n section changes so that the charging and discharging (closed circuit) potentials of the n section become equal, each component of each section does not appear in the external voltage.
  • Positive electrode potential of n part equilibrium potential ⁇ SOC adjustment voltage of n part active material non-uniformity ⁇ n part reaction surface ion concentration correction voltage n part positive electrode potential, equilibrium potential, n part active material non-uniform SOC adjustment voltage, n part
  • the reaction surface ion concentration correction voltage is not the same, but a peculiar value of each n part, but since each part is connected in parallel, the positive electrode potential becomes the maximum potential difference with respect to the negative electrode. That is, even if there are different equilibrium potentials in the electrodes, that is, parts with different thermodynamic internal energies, the positive electrode potential appears only the highest potential with respect to the negative electrode. Considerations and proposals regarding this potential are novel theories, and are very important in constructing the present invention.
  • the electrode potential of the electrochemical reaction on the surface in contact with the electrolyte that is, the cell voltage appears. If the m-th potential in contact with the electrolytic solution is the highest in the n-part, the potential of the positive electrode is the m-th potential regardless of the potentials of other locations.
  • the charge carrier ions such as lithium ions in the layered compound are generated by electrostatic force. It is stored and stored in the void. Electricity is stored and charged by the "cantilever principle" in equilibrium with the injected electrons at a position separated by several nanometers along the wall of the cavity.
  • Charge carrier ions in the electrolytic solution or solid electrolyte are intercalated into the layered compound by oxidation-reduction reactions so as to replenish the charge carrier ions depleted in the layered compound. Any reaction that has an oxidation-reduction potential, that is, an electrode reaction potential, by insertion may be used.
  • lithium cobalt oxide used in current lithium-ion batteries has the following reaction formula.
  • the storage reaction in the void is represented by the following reaction formula.
  • the value of x is determined by the size of the voids, and according to the results of computational chemistry in Non-Patent Documents 1 and 2, a diameter of 4 nm or more is preferable, but since they are arranged along the walls, if they are too large, the central portion becomes redundant. Since it becomes a large space, the volumetric efficiency becomes worse.
  • the energy density is at least twice that of the current positive electrode material, and the positive electrode potential is the oxidation-reduction potential of lithium cobalt oxide, satisfying the requirements for electric vehicle batteries. can do Each discharge after the first discharge results in the same reaction.
  • the charge carrier ions present in the layered compound are desorbed from the layered compound into the electrolytic solution or solid electrolyte by oxidation-reduction reactions.
  • Any reaction that has an oxidation-reduction potential that is, an electrode reaction potential, may be used.
  • electron deficiencies are injected around the voids of the layered compound, and the charge carrier ions in the voids are pushed out by electrostatic repulsion, replenishing the decrease in the charge carrier ions in the layered compound.
  • Charge carrier ions are inserted into the layered compound so as to
  • the storage reaction in the void is represented by the following reaction formula. ⁇ Void xLi + xe - > + x (electron deficiency) + ⁇ Void/x (electron deficiency) + >+xLi + +e -
  • voids are provided in existing layered compounds such as lithium cobalt oxide, lithium nickel-cobalt-manganese oxide, lithium nickel manganese oxide, lithium iron phosphate, and the like, as illustrated in FIG.
  • Charge carrier ions such as lithium ions
  • the charge carrier ions in the voids come into contact with the electrolyte or solid electrolyte via the layered compound and undergo a charge transfer reaction. Since it becomes the redox potential of the compound, the energy density can be increased.
  • By optimizing the voids it is possible to store more than twice as much electric charge as current layered metal oxides.
  • the surface of the porous structure having voids facing the electrolytic solution or solid electrolyte is coated with an existing layered compound, resulting in intercalation/deintercalation as illustrated in FIG.
  • Charge carrier ions can be incorporated into the porous structure at the potential of the layered compound having an oxidation-reduction potential of .
  • Charge carrier ions can be stored in the voids of the porous body structure with electron storage properties such as hard carbon and soft carbon, so it can store much more charge than the current layered metal oxide such as lithium cobalt oxide.
  • Non-Patent Documents 1 and 2 can do Although the potential of the charge carrier ions in the voids estimated from the calculation results of the stabilization energy in Non-Patent Documents 1 and 2 is very low, it passes through the layered compound, so it becomes the oxidation-reduction reaction potential of the layered compound. .
  • charges such as lithium ions are generated in the voids formed inside the layered compound such as layered metal oxides or layered metal phosphates having oxidation-reduction reaction potentials.
  • It is a positive electrode active material that occludes and stores carrier ions.
  • a storage battery composed of the positive electrode active material.
  • charge carrier ions Prior to use as a storage battery, charge carrier ions are stored and accumulated in the positive electrode active material voids by initial discharge. The initial discharge may be performed for the positive electrode active material alone before incorporating the positive electrode into the storage battery.
  • the voids capable of storing and accumulating charge carrier ions shown in the schematic diagram of FIG. 1 in the present invention can be created by insufficient sintering of conventional layered metal oxides. Furthermore, it can be formed by controlling the temperature and time so that only the surface is completely sintered when the sintered body is pulverized and refired to form granules. Amorphization by quenching, which tends to create voids, can also be applied.
  • voids capable of storing and accumulating charge carrier ions shown in the schematic diagram of FIG.
  • voids can be formed relatively easily, and voids can be formed inside the polycrystalline grains by completely sintering only the grain surfaces.
  • charge carrier ions such as lithium ions are stored in voids of a porous structure such as hard carbon or soft carbon.
  • a porous structure such as hard carbon or soft carbon.
  • the present invention can store two to several times as many charge carrier ions at the same potential as existing layered metal oxides, making it ideal for use as a battery for electric vehicles, and can extend the current one-charge driving distance by more than double. , the performance of which is equivalent to that of gasoline-powered vehicles, which will greatly contribute to the electrification of automobiles and contribute to the realization of a decarbonized society.
  • the present invention can store two to several times as many charge carrier ions at the same potential as the current layered metal oxide, it can be applied to a stationary power storage system, the number of storage batteries in the system can be halved, and the system price of the storage battery can be halved. Therefore, it can greatly contribute to the spread of stationary power storage systems that are installed alongside renewable energy power generation. As a result, it will support the spread of renewable energy and contribute to the realization of a decarbonized society.

Abstract

Lithium-ion storage batteries, which are widely used as storage batteries for portable phones, lack energy density as storage batteries for electric vehicles and cannot meet the one-charge travel distance required by private vehicles, requiring higher energy density, especially of positive-electrode active materials. The problem is to provide a positive-electrode active material having an oxidation-reduction potential equal to that of positive-electrode active materials in current lithium-ion storage batteries and several times the storage capacity in order to achieve a higher energy density of positive-electrode active materials. By providing a void in a compound having oxidation-reduction potential through the insertion and desorption of charge carrier ions well-known in the existing art, and occluding and storing charge carrier ions in the void, the problem of providing a high-energy-density positive-electrode active material that satisfies both conditions of high capacity and high voltage can be solved.

Description

正極及び蓄電池positive electrode and storage battery
　本発明は、蓄電池の正極活物質に関する。また、その正極活物質により構成された蓄電池に関する。 The present invention relates to a positive electrode active material for storage batteries. Moreover, it is related with the storage battery comprised by the positive electrode active material.
　１９９１年にソニー株式会社が製品化したリチウムイオン蓄電池は高いエネルギー密度を有するために、ノートパソコン、携帯電話などで広く使われ、最近では電気自動車用電池として脚光を浴びている。しかし、ガソリン自動車はガソリンタンク満タンで１０００ｋｍ以上走行することが出来るが、現在市販されている電気自動車の日産自動車製リーフの１充電走行距離はカタログ値４００ｋｍで、自家用車として購入するには走行距離が不足している。従って、1充電で１０００ｋｍ走行できる、つまり2倍以上のエネルギー密度を有する革新電池の開発が望まれている。 　The lithium-ion storage battery, which was commercialized by Sony Corporation in 1991, has a high energy density and is widely used in laptop computers, mobile phones, etc. Recently, it has been in the limelight as a battery for electric vehicles. However, gasoline cars can run more than 1000km with a full tank of gasoline, but the mileage of one charge of the Nissan Leaf, an electric car currently on the market, is 400km in the catalog value. Insufficient distance. Therefore, it is desired to develop an innovative battery that can run 1000km on one charge, that is, has more than twice the energy density.
　リチウムイオンが充放電に伴い挿入・脱離する層状金属酸化物が、リチウムイオン蓄電池の正極活物質として使われているが、最近の研究で、結晶を構成する金属イオンの酸化還元量を大幅に上回る容量が得られた実験結果が発表された。この大幅に得られた容量は正極過剰容量と呼ばれ、現行のコバルト・ニッケル・マンガン3元系層状金属酸化物１６０ｍＡｈ／ｇの2倍以上を目標に多くの研究がされている。過剰容量の原因は結晶を構成する酸素原子が通常のマイナス2価から過酸化状態のマイナス1価になっているためと考えられている。しかし、過酸化状態の酸素は結合力が弱く結晶から抜け出し、構造が破壊され蓄電池として十分な充放電サイクルをできない。また、過剰に結晶取り込まれたリチウムイオンの結晶中の占有位置も明確には出来ていない。 Layered metal oxides, into which lithium ions are intercalated and deintercalated during charging and discharging, are used as positive electrode active materials for lithium-ion batteries. Experimental results showing higher capacities have been published. This greatly obtained capacity is called positive electrode excess capacity, and much research is being conducted with the goal of making it more than twice the current cobalt-nickel-manganese ternary layered metal oxide of 160 mAh/g. It is thought that the cause of the excess capacity is that the oxygen atoms that make up the crystal have changed from the normal minus 2 valence to the minus 1 valence in the peroxide state. However, oxygen in a peroxide state is weak in binding force and escapes from the crystal, destroying the structure and preventing a sufficient charge-discharge cycle as a storage battery. In addition, the occupied positions in the crystal of lithium ions excessively incorporated into the crystal have not been clarified.
　両極に挿入型のカーボンを用いるデュアルカーボン電池で、多孔体構造である正負極活物質の細孔を模式図として筒状に描くと図２のようになる。両極の表面は電解液との反応で形成されたＳＥＩ（固体電解質界面）または、リチウムイオンのような電荷担体イオンは通過させるが、エチレンカーボネートのような溶媒を通過させない「篩膜」に覆われており、細孔内は溶媒がない状態である。充電により負極活物質に電子が注入され、正極活物質には電子欠損が注入され、その電荷と電気的中性が保たれるように負極活物質細孔には正イオンが、正極活物質細孔には負イオンが貯蔵・蓄電される。反応式は次式になる。
　正極反応　:Ｃ＋（Ｘ-溶媒）　　　⇔　ＣＸ-＋（溶媒）＋（電子欠損）+
　負極反応　:Ｃ＋（Ｌｉ +溶媒）　　⇔　ＣＬｉ +＋（溶媒）＋ｅ-　
　全電池反応:２Ｃ＋（Ｘ-溶媒）＋（Ｌｉ +溶媒）⇔ＣＸ-＋ＣＬｉ +＋２（溶媒）
充電後には電解液中に正負イオンはほとんどなくなり、電解液中に存在する正負イオンの量で、電池の充放電量が制限される。電解液中に存在する正負イオンは電解質塩を溶媒に溶解することで得られるので、固体活物質中に正イオンを貯蔵・蓄電する現行のリチウムイオン電池を上回ることは出来ないことは明らかである。 In a dual carbon battery that uses insertion type carbon for both electrodes, the pores of the positive and negative electrode active materials, which have a porous structure, are drawn in a cylindrical shape as shown in FIG. The surfaces of both electrodes are covered by an SEI (solid electrolyte interface) formed by reaction with the electrolyte or a "sieve membrane" that allows the passage of charge carrier ions such as lithium ions but blocks the passage of solvents such as ethylene carbonate. , and there is no solvent in the pores. Electrons are injected into the negative electrode active material by charging, and electron deficiencies are injected into the positive electrode active material. Negative ions are stored and charged in the pores. The reaction formula is as follows.
Cathode reaction: C + (X - solvent) ⇔ CX - + (solvent) + (electron deficiency) +
Anode reaction: C + (L i + solvent) ⇔ CL i + + (solvent) + e -
Full cell reaction: 2C + (X - solvent) + (L i + solvent) <-> CX - + CL i + +2 (solvent)
After charging, there are almost no positive and negative ions in the electrolyte, and the amount of positive and negative ions present in the electrolyte limits the amount of charging and discharging of the battery. Since the positive and negative ions present in the electrolyte are obtained by dissolving the electrolyte salt in a solvent, it is clear that it cannot surpass current lithium-ion batteries that store and charge positive ions in solid active materials. .
　リチウム金属を負極とし現行負極のグラファイトを正極として放電出来ることは、カーボン極のＳＥＩ形成処理などのためにリチウムイオンを予め挿入する「プレドープ」と呼ばれる手法として周知かつ実用化されている。この反応は可逆性があり、負極ではリチウム金属析出反応、正極ではリチウムイオン挿入・脱離反応が起きる。反応式は次式になる。　　
　正極反応　：　ｎＣ＋｛Ｌｉ ＋（溶媒）｝＋ｅー　⇔　ＬｉＣｎ＋（溶媒）
　負極反応　：　Ｌｉ（metal）＋（溶媒）　⇔　｛Ｌｉ ＋（溶媒）｝＋ｅー
　全電池反応：　Ｌｉ（metal）＋ｎＣ　⇔　ＬｉＣｎ
プレドープしたカーボンを正負両極として電池を構成すると、高い電位のカーボン極が正極となり、低い電位のカーボン極が負極となる。図３はその反応機構を模式図で示した。反応式は次式になる。
　正極反応　：　ｍＣ＋｛Ｌｉ +（溶媒）｝＋ｅ-　⇔　ＬｉＣｍ＋（溶媒）　
　負極反応　：　２ＬｉＣｎ＋（溶媒）＋（ｍ－２ｎ）Ｃ　
　　　　　　　　　　　　　　　　　⇔　ＬｉＣｍ＋｛Ｌｉ +（溶媒）｝＋ｅ-
　全電池反応：　ＬｉＣｎ　＋（ｍ―ｎ）Ｃ　⇔　ＬｉＣｍ（ｎ＜ｍ）
先行技術文献の特許文献１および特許文献２を参考に、リチウムイオンは通過できるが溶媒および負イオンは通過できない篩膜を用いれば、負極はカーボン数ｎ＝２つまりＬiＣ２まで挿入・蓄電することが出来、正極はリチウムイオンが挿入されていない状態まで充電することが出来、その中間まで放電することが出来る。現行グラファイトの理論容量は３７２ｍＡｈで、非特許文献１、非特許文献２および非特許文献３によれば、篩膜を用いることで、ソフトカーボン・ハードカーボンのような多孔体構造カーボンでは、重量当たり容量はグラファイトの約3倍、１０００ｍＡｈとなり、体積当り容量は約２倍、７００ｍＡｈとなり、目標とする現行の2倍の高容量正極を実現できる。しかしながら、両極が同じ脱挿入反応のために、正負極の電位差つまり蓄電池電圧は、現行リチウムイオン蓄電池の半分程度しかなく、エネルギー密度向上にはならない。 The fact that lithium metal can be used as the negative electrode and graphite, which is the current negative electrode, can be discharged as the positive electrode is well known and put into practical use as a technique called "pre-doping" in which lithium ions are inserted in advance for SEI formation processing of the carbon electrode. This reaction is reversible, and a lithium metal deposition reaction occurs at the negative electrode, and a lithium ion insertion/extraction reaction occurs at the positive electrode. The reaction formula is as follows.
Cathode reaction: nC + {Li + (solvent)} + e - ⇔ LiC n + (solvent)
Anode reaction: L i (metal) + (solvent) ⇔ {L i + (solvent)} + e-
Whole cell reaction: Li ( metal) + nC ⇔ LiC n
When a battery is constructed with predoped carbon as both positive and negative electrodes, the carbon electrode with a higher potential becomes the positive electrode and the carbon electrode with a lower potential becomes the negative electrode. FIG. 3 schematically shows the reaction mechanism. The reaction formula is as follows.
Cathode reaction: mC + {L i + (solvent)} + e − ⇔ L i C m + (solvent)
Anode reaction: 2L i C n + (solvent) + (m-2n) C　
⇔ L i C m + {L i + (solvent)} + e -
Whole cell reaction: L i C n + (mn) C ⇔ L i C m (n<m)
With reference to Patent Documents 1 and 2 of prior art documents, if a sieve membrane that allows lithium ions to pass through but not the solvent and negative ions to pass through is used, the negative electrode can insert and store electricity up to the number of carbon n = 2, that is, LiC 2 . The positive electrode can be charged to a state where lithium ions are not inserted, and can be discharged to an intermediate state. The theoretical capacity of current graphite is 372 mAh. The capacity is about three times that of graphite, or 1000 mAh, and the capacity per volume is about two times, or 700 mAh. However, since the deinsertion reaction is the same at both electrodes, the potential difference between the positive and negative electrodes, that is, the storage battery voltage, is only about half that of the current lithium ion storage battery, and the energy density cannot be improved.
　図４は非特許文献４を参照に作図した。充電時には、リチウムイオンが正極コバルト酸リチウムから固体電解質ＬＡＴＳＰＯ内を負極集電体Ｐｔに向かって移動し、Ｐｔから７００ｎｍ程度でリチウムイオンが非常に多い分布領域、その手前２μm程度にリチウムイオンが少し存在する分布領域が出来る。図では不連続に描かれているが、連続的に濃度が変化し、濃度勾配は指数関数のようになる。高濃度に分布された７００ｎｍの領域のリチウムイオンが充放電に伴い増減することから、「その場形成負極」と名付けられた。 Figure 4 was drawn with reference to Non-Patent Document 4. During charging, lithium ions move from the positive electrode lithium cobaltate to the negative electrode current collector Pt in the solid electrolyte LATSPO. An existing distribution area can be created. Although it is drawn discontinuously in the figure, the concentration changes continuously and the concentration gradient becomes like an exponential function. It was named "in-situ formation negative electrode" because lithium ions in the region of 700 nm distributed in high concentration increase and decrease with charging and discharging.
　充放電はリチウム金属の析出電位ではなく、リチウムイオンが固体電解質に挿入脱離しているので、非特許文献１及び２の計算化学で実証された「片持ち論」に基づくリチウムイオンの貯蔵・蓄電である。図５の左図は、初充電時のリチウムイオン挿入で結晶に歪が生じ、固体電解質内に形成されたナノサイズの空隙・隙間・割れ目がある状態図である。発表者の説明では、充放電後の透過型顕微鏡による観察で空隙の存在は認められるが、その空隙にリチウムイオンが存在することは、計測分解能が不足し測定不能であるとのことであった。その空隙に挿入・脱離することでリチウムイオンの充放電が起きている。非特許文献１、２及び３に記載された計算化学で実証された「片持ち論」は、カーボンナノチューブに限らず、電子電導性を有する物質に形成されたあらゆる形状の空隙に定性的には成立する。図５の右図は空隙を拡大した図で、空隙の壁に沿ってリチウムイオンが一定の間隔に並んでいる。空隙の中央に挟まれてではなく、また複数個が集まってクラスターになることもない。初充電時のリチウムイオンの挿入で結晶に歪が生じ空隙が形成され、さらには結晶歪により、電子電導性も出現する。非特許文献１及び２におけるカーボンナノチューブが、「空隙」と電子電導を発現した固体電解質に置き換わっている。反応式は次式のようになる。充放電も同じ反応式になる。
　負極充電（形成）反応：　Ｌｉ+＋＜空隙＞＋ｅ-　⇔　＜空隙・Ｌｉ+・ｅ-＞　
正極負極はどちらの電位が高いかで決められることで、可逆反応であれば、相手次第では正極にも負極にもなる。「その場負極」も相手極が金属リチウムであれば、「その場正極」になる。 Since the charging and discharging is not the deposition potential of lithium metal, but the lithium ions are inserted into and detached from the solid electrolyte, storage and storage of lithium ions based on the "cantilever theory" demonstrated by computational chemistry in Non-Patent Documents 1 and 2 is. The left diagram of FIG. 5 is a state diagram showing nano-sized voids, crevices, and cracks formed in the solid electrolyte due to strain in the crystal due to the insertion of lithium ions during the initial charge. According to the presenter's explanation, the presence of voids can be observed by observation with a transmission microscope after charging and discharging, but the existence of lithium ions in the voids cannot be measured due to insufficient measurement resolution. . Lithium ions are charged and discharged by inserting/deintercalating them into and out of the voids. The "cantilever theory" demonstrated by computational chemistry described in Non-Patent Documents 1, 2 and 3 is not limited to carbon nanotubes, but qualitatively To establish. The right view of FIG. 5 is an enlarged view of the void, and lithium ions are arranged at regular intervals along the wall of the void. They are not sandwiched in the center of the gap, nor are they clustered together. The intercalation of lithium ions during the initial charge causes strain in the crystal, forming voids. The carbon nanotubes in Non-Patent Documents 1 and 2 are replaced by solid electrolytes exhibiting "voids" and electronic conductivity. The reaction formula is as follows. Charging and discharging also follow the same reaction formula.
Negative charge (formation) reaction: Li + + <void> + e - ⇔ <void Li + e - >
The positive and negative electrodes are determined by which side has the higher potential, so in the case of a reversible reaction, depending on the partner, it can be either the positive electrode or the negative electrode. The "in-situ negative electrode" also becomes an "in-situ positive electrode" if the mating electrode is metallic lithium.
特許第５０６２９８９号公報Japanese Patent No. 5062989
特許第５１３４２５４号公報Japanese Patent No. 5134254
　リチウムイオン2次電池の蓄電エネルギーは、蓄電量と電圧との積であり、背景技術で解説したように、蓄電量を現行の3元系層状金属酸化物の１６０ｍＡｈ／ｇの２から３倍に増やすことは従来の理論・技術で実現できるが、同じ材料で現行のリチウムイオン電池と同等の電圧３．６Ｖを得られる理論・技術はなかった。 The stored energy of a lithium-ion secondary battery is the product of the amount of stored electricity and the voltage. Conventional theory and technology can be used to increase the capacity, but there was no theory or technology that could obtain a voltage of 3.6 V, which is equivalent to that of current lithium-ion batteries, using the same materials.
　高容量と高電圧を実現するためには、蓄電方法について新しい電池理論が必要であり、本発明はその理論と手段を提供する。 In order to achieve high capacity and high voltage, a new battery theory is necessary for the storage method, and the present invention provides the theory and means.
　正極をｎ個の要素に分割する。ｎ個の分割は仮想上で分割したので、特定の場所である必要はなく、均等である必要はなく、任意で良く、ｎ数も任意であり無限でも良い。ｎ部個々の電気的特性は次のように書ける。
　ｎ部の充放電（閉路）電位＝平衡電位±｛ｎ部の（電子抵抗＋イオン移動抵抗）｝＊｛ｎ部の電流｝±ｎ部の電荷移動過電圧±ｎ部活物質不均一性のＳＯＣ調整電圧±ｎ部の反応面イオン濃度補正電圧
分割したｎ部は並列に接続されているので、負極に対しｎ部の充放電（閉路）電位は１～ｎで全て同一である。ｎ部の電子抵抗、ｎ部のイオン移動抵抗、ｎ部の電荷移動過電圧、ｎ部の活物質不均一性のＳＯＣ調整電圧、ｎ部の反応面イオン濃度補正電圧はｎ部で全て異なるが、ｎ部の充放電（閉路）電位が等しくなるようにｎ部の電流が変化するので、各部の各構成要素を外部電圧には現れない。 Divide the positive electrode into n elements. Since the n divisions are made virtually, they do not have to be in a specific place, they do not have to be even, they may be arbitrary, and the number of n may be arbitrary or infinite. The electrical characteristics of each n part can be written as follows.
Charge/discharge (closing) potential of n part = equilibrium potential ± {(electronic resistance + ion transfer resistance) of n part} * {current of n part} ± charge transfer overvoltage of n part ± SOC adjustment of n part active material heterogeneity Since the n parts obtained by dividing the reaction surface ion concentration correction voltage of ±n parts are connected in parallel, the charging/discharging (closed circuit) potentials of the n parts with respect to the negative electrode are all the same from 1 to n. The electronic resistance of the n part, the ion transfer resistance of the n part, the charge transfer overvoltage of the n part, the SOC adjustment voltage of the active material non-uniformity of the n part, and the reaction surface ion concentration correction voltage of the n part are all different in the n part, Since the current in the n section changes so that the charging and discharging (closed circuit) potentials of the n section become equal, each component of each section does not appear in the external voltage.
　電流を遮断すると、電流は「０」になるので、ｎ部の電子抵抗とｎ部のイオン移動抵抗にｎ部の電流を乗じた値は直ちに「０」になり、電流の対数関数である電荷移動過電圧も数秒後には「０」になり、ｎ部の正極電位は次式で表される。
　　　ｎ部の正極電位＝平衡電位±ｎ部活物質不均一性のＳＯＣ調整電圧
　　　　　　　　　　　　±ｎ部反応面イオン濃度補正電圧
ｎ部の正極電位、平衡電位、ｎ部活物質不均一性のＳＯＣ調整電圧、ｎ部反応面イオン濃度補正電圧は、同一ではなく、各ｎ部の固有値であるが、その各部が並列に接続しているので、正極電位は負極を基準にして、最も大きな電位差となる電位になる。つまり、電極内に異なる平衡電位、つまり熱力学的内部エネルギーの異なる部分があったとしても、正極電位は負極に対し最も高い電位しか現れない。この電位についての考察・提案は新規な理論であり、本発明を構成する上で非常に重要である。 When the current is cut off, the current becomes "0", so the value obtained by multiplying the electronic resistance of the n part and the ionic transfer resistance of the n part by the current of the n part immediately becomes "0", and the charge, which is a logarithmic function of the current The moving overvoltage also becomes "0" after several seconds, and the positive electrode potential of the n part is expressed by the following equation.
Positive electrode potential of n part = equilibrium potential ± SOC adjustment voltage of n part active material non-uniformity ± n part reaction surface ion concentration correction voltage n part positive electrode potential, equilibrium potential, n part active material non-uniform SOC adjustment voltage, n part The reaction surface ion concentration correction voltage is not the same, but a peculiar value of each n part, but since each part is connected in parallel, the positive electrode potential becomes the maximum potential difference with respect to the negative electrode. That is, even if there are different equilibrium potentials in the electrodes, that is, parts with different thermodynamic internal energies, the positive electrode potential appears only the highest potential with respect to the negative electrode. Considerations and proposals regarding this potential are novel theories, and are very important in constructing the present invention.
　電位の異なる成分があっても、電極電位を示すためには電荷移動反応が起きるつまり電解質との接触が必要である。異なる成分があっても電解液と接触している表面での電気化学反応の電極電位つまり電池電圧が出現する。電解液に接触しているｍ番目の電位が、ｎ部の中で一番高いとすれば、他の箇所の電位に拘わらず、正極の電位はm番目の電位である。 Even if there are components with different potentials, in order to indicate the electrode potential, a charge transfer reaction occurs, that is, contact with the electrolyte is necessary. Even if there are different components, the electrode potential of the electrochemical reaction on the surface in contact with the electrolyte, that is, the cell voltage appears. If the m-th potential in contact with the electrolytic solution is the highest in the n-part, the potential of the positive electrode is the m-th potential regardless of the potentials of other locations.
　図１に示すように、放電状態で製造された酸化還元電位を有する層状化合物内に空隙があり、初放電つまり電子を注入すると、層状化合物内のリチウムイオンなどの電荷担体イオンが静電力により、空隙内に貯蔵・蓄電される。空隙の壁に沿って数ｎｍ離れた位置に、注入された電子と釣り合って、「片持ち論」により貯蔵・蓄電される。層状化合物内で減少した電荷担体イオンを補充するように、電解液あるいは固体電解質中の電荷担体イオンが酸化還元反応で層状化合物内に挿入される。挿入により酸化還元電位つまり電極反応電位を有する反応であれば何でもよいが、例えば、現行リチウムイオン電池で使われているコバルト酸リチウムで例示すると、次式のような反応式になる。　　　　
　　　Ｌｉ ＋＋２Ｌｉ0.05ＣｏＯ2　＋　ｅ―　 　⇔　２ＬｉＣｏＯ2
空隙における貯蔵反応は次式の反応式になる。
　　　ｘＬｉ+＋＜空隙＞＋ｘｅ-　⇔　＜空隙・ｘＬｉ+・ｘｅ-＞
ｘの値は空隙の大きさにより決定されるが、非特許文献１、２の計算化学での結果からは直径４ｎｍ以上が良いが、壁に沿って配列するので、大き過ぎると中央部は余分な空間になるので体積効率は悪くなる。ｘ＝１でも、現行の正極材料の2倍になり、かつ正極電位はコバルト酸リチウムの酸化還元電位であるから、エネルギー密度は少なくとも2倍以上になり、電気自動車用電池としての要求基準を満たすことが出来る。初放電後の毎回の放電は同じ反応になる。 As shown in FIG. 1, there are voids in the layered compound with redox potential produced in the discharged state, and when the first discharge, that is, the injection of electrons, the charge carrier ions such as lithium ions in the layered compound are generated by electrostatic force. It is stored and stored in the void. Electricity is stored and charged by the "cantilever principle" in equilibrium with the injected electrons at a position separated by several nanometers along the wall of the cavity. Charge carrier ions in the electrolytic solution or solid electrolyte are intercalated into the layered compound by oxidation-reduction reactions so as to replenish the charge carrier ions depleted in the layered compound. Any reaction that has an oxidation-reduction potential, that is, an electrode reaction potential, by insertion may be used. For example, lithium cobalt oxide used in current lithium-ion batteries has the following reaction formula.
L i + +2 L i0.05 Co O 2 + e - 　 ⇔ 2LiCoO2 _
The storage reaction in the void is represented by the following reaction formula.
xLi + + <gaps> + xe - ⇔ <gaps xLi + xe - >
The value of x is determined by the size of the voids, and according to the results of computational chemistry in Non-Patent Documents 1 and 2, a diameter of 4 nm or more is preferable, but since they are arranged along the walls, if they are too large, the central portion becomes redundant. Since it becomes a large space, the volumetric efficiency becomes worse. Even with x = 1, the energy density is at least twice that of the current positive electrode material, and the positive electrode potential is the oxidation-reduction potential of lithium cobalt oxide, satisfying the requirements for electric vehicle batteries. can do Each discharge after the first discharge results in the same reaction.
　充電時には図1の下図に示すように、層状化合物内に存在する電荷担体イオンは、電解液あるいは固体電解質内に酸化還元反応で層状化合物から脱離する。脱離により酸化還元電位つまり電極反応電位を有する反応であれば何でもよいが、例えば、現行リチウムイオン電池で使われているコバルト酸リチウムで例示すると、次式のような反応式になる。　　　　
　　　２ＬｉＣｏＯ2　⇔　Ｌｉ ＋＋２Ｌｉ0.05ＣｏＯ2　＋ｅ―　
上式の充電反応と並行して、層状化合物の空隙周辺には電子欠損が注入され、空隙内の電荷担体イオンは静電反発力で押し出され、層状化合物内中の電荷担体イオンの減少を補充するように電荷担体イオンが層状化合物に挿入される。空隙における貯蔵反応は次式の反応式になる。
　　　＜空隙・ｘＬｉ+・ｘｅ-＞＋ｘ(電子欠損)＋
　　　　　　　　　　　　⇔＜空隙・ｘ(電子欠損) ＋＞＋ｘＬｉ+＋ｅ― During charging, as shown in the lower diagram of FIG. 1, the charge carrier ions present in the layered compound are desorbed from the layered compound into the electrolytic solution or solid electrolyte by oxidation-reduction reactions. Any reaction that has an oxidation-reduction potential, that is, an electrode reaction potential, may be used.
2L i CoO 2 ⇔ Li + +2L i 0.05 CoO 2 + e -
In parallel with the charging reaction of the above formula, electron deficiencies are injected around the voids of the layered compound, and the charge carrier ions in the voids are pushed out by electrostatic repulsion, replenishing the decrease in the charge carrier ions in the layered compound. Charge carrier ions are inserted into the layered compound so as to The storage reaction in the void is represented by the following reaction formula.
<Void xLi + xe - > + x (electron deficiency) +
⇔<Void/x (electron deficiency) + >+xLi + +e -
　本発明に因れば、既存のコバルト酸リチウム、ニッケル・コバルト・マンガン酸リチウム、ニッケルマンガン酸リチウム、リン酸鉄リチウムなどの層状化合物に空隙を設けることで、図１に図説するように、空隙内に、例えばリチウムイオンなどの電荷担体イオンを貯蔵でき、その空隙内の電荷担体イオンはその層状化合物を経由して電解液あるいは固体電解質と接触し電荷移動反応をし、電極反応電位はその層状化合物の酸化還元電位となるので、エネルギー密度を増大できる。空隙の最適化をすることで、現行の層状金属酸化物の2倍以上の電荷を蓄電することが出来る。 According to the present invention, voids are provided in existing layered compounds such as lithium cobalt oxide, lithium nickel-cobalt-manganese oxide, lithium nickel manganese oxide, lithium iron phosphate, and the like, as illustrated in FIG. Charge carrier ions, such as lithium ions, can be stored inside the cavity, and the charge carrier ions in the voids come into contact with the electrolyte or solid electrolyte via the layered compound and undergo a charge transfer reaction. Since it becomes the redox potential of the compound, the energy density can be increased. By optimizing the voids, it is possible to store more than twice as much electric charge as current layered metal oxides.
　　　　本発明に因れば、電解液または固体電解質に面している空隙を有する多孔体構造体の表面に、既存の層状化合物を被覆することで、図６に図説するように、挿入・脱離で酸化還元電位を有する層状化合物の電位で電荷担体イオンを多孔体構造に取り込むことが出来る。ハードカーボン・ソフトカーボンのような電子電槽性を有する多孔体構造の空隙に電荷担体イオンを貯蔵することが出来るので、現行のコバルト酸リチウムなどの層状金属酸化物よりはるかに多くの電荷を蓄電することが出来る。なお、非特許文献１及び２の安定化エネルギーの計算結果から推定される空隙内の電荷担体イオンの電位は非常に低いが、層状化合物を経由するので、層状化合物が有する酸化還元反応電位になる。 According to the present invention, the surface of the porous structure having voids facing the electrolytic solution or solid electrolyte is coated with an existing layered compound, resulting in intercalation/deintercalation as illustrated in FIG. Charge carrier ions can be incorporated into the porous structure at the potential of the layered compound having an oxidation-reduction potential of . Charge carrier ions can be stored in the voids of the porous body structure with electron storage properties such as hard carbon and soft carbon, so it can store much more charge than the current layered metal oxide such as lithium cobalt oxide. can do Although the potential of the charge carrier ions in the voids estimated from the calculation results of the stabilization energy in Non-Patent Documents 1 and 2 is very low, it passes through the layered compound, so it becomes the oxidation-reduction reaction potential of the layered compound. .
空隙を有する層状金属酸化物充放電機構解説模式図Schematic diagram of charging/discharging mechanism of layered metal oxide with voids 篩膜付きデュアルカーボン蓄電池充放電機構解説模式図Schematic diagram explaining charge/discharge mechanism of dual carbon storage battery with sieve membrane 両極カーボンリチウムイオン蓄電池充放電機構解説模式図Bipolar Carbon Lithium Ion Battery Charging and Discharging Mechanism Explanation Schematic Diagram その場形成負極模式図Schematic diagram of in-situ formed negative electrode その場形成負極拡大模式図Enlarged schematic diagram of in-situ formed negative electrode 層状金属酸化物被覆電子電導性多孔体構造体模式図Schematic diagram of layered metal oxide-coated electronically conductive porous structure
　図１の模式図に示すように、リチウムイオン挿入脱離に伴い、酸化還元反応電位を有する層状金属酸化物あるいは層状金属リン酸物などの層状化合物内部に形成した空隙に、リチウムイオンなどの電荷担体イオンを吸蔵・蓄電する正極活物質である。及びその正極活物質で構成された蓄電池である。蓄電池としての使用前に初放電により正極活物質空隙に電荷担体イオンを貯蔵・蓄電する。初放電は蓄電池に正極を組み込む前に正極活物質単体で行っても良い。 As shown in the schematic diagram of FIG. 1, with the intercalation and deintercalation of lithium ions, charges such as lithium ions are generated in the voids formed inside the layered compound such as layered metal oxides or layered metal phosphates having oxidation-reduction reaction potentials. It is a positive electrode active material that occludes and stores carrier ions. and a storage battery composed of the positive electrode active material. Prior to use as a storage battery, charge carrier ions are stored and accumulated in the positive electrode active material voids by initial discharge. The initial discharge may be performed for the positive electrode active material alone before incorporating the positive electrode into the storage battery.
　本発明における図１の模式図で示す電荷担体イオンを貯蔵・蓄電できる空隙は、従来の層状金属酸化物を不十分な焼成で作成することができる。さらに、焼結体を微粉砕し、再焼成して造粒する時に表面だけが完全に焼結するように温度・時間を制御することで形成することが出来る。空隙が出来易い急冷法などに因るアモルファス化なども適用できる。 The voids capable of storing and accumulating charge carrier ions shown in the schematic diagram of FIG. 1 in the present invention can be created by insufficient sintering of conventional layered metal oxides. Furthermore, it can be formed by controlling the temperature and time so that only the surface is completely sintered when the sintered body is pulverized and refired to form granules. Amorphization by quenching, which tends to create voids, can also be applied.
　本発明における図１の模式図で示す電荷担体イオンを貯蔵・蓄電できる空隙は、層状化合物粒子を機械的衝突エネルギー（メカニカルミーリング法）で焼成あるいは造粒する時に衝突数・衝突エネルギー・温度・時間を制御すると、比較的に容易に空隙が出来、粒子表面だけを完全に焼結させることで、多結晶粒子内部に空隙を形成することが出来る。 The voids capable of storing and accumulating charge carrier ions shown in the schematic diagram of FIG. By controlling , voids can be formed relatively easily, and voids can be formed inside the polycrystalline grains by completely sintering only the grain surfaces.
　本発明で上記層状金属酸化物に空隙を設ける方法よりも多くの電荷担体イオンを蓄電するためには、ハードカーボンあるいはソフトカーボンなどの多孔体構造の空隙に、リチウムイオンなどの電荷担体イオンを貯蔵・蓄電する方法がある。この場合には、図６に図説するように、多孔体構造の周囲・表面を、挿入・脱離反応で酸化還元電位を有する層状化合物で被覆することで実施できる。 In order to store more charge carrier ions than the method of providing voids in the layered metal oxide according to the present invention, charge carrier ions such as lithium ions are stored in voids of a porous structure such as hard carbon or soft carbon.・There is a way to store electricity. In this case, as illustrated in FIG. 6, it can be carried out by coating the periphery/surface of the porous body structure with a layered compound having an oxidation-reduction potential upon insertion/desorption reaction.
　本発明は現行の層状金属酸化物と同じ電位で、電荷担体イオンを2倍から数倍蓄電できるので、電気自動車用電池として最適で、現行の一充電走行距離を2倍以上延長することが出来、ガソリン自動車と同等の性能となり、自動車の電動化に大きく貢献し、脱炭素社会の実現に貢献する。 The present invention can store two to several times as many charge carrier ions at the same potential as existing layered metal oxides, making it ideal for use as a battery for electric vehicles, and can extend the current one-charge driving distance by more than double. , the performance of which is equivalent to that of gasoline-powered vehicles, which will greatly contribute to the electrification of automobiles and contribute to the realization of a decarbonized society.
本発明は現行の層状金属酸化物と同じ電位で、電荷担体イオンを2倍から数倍蓄電できるので、定置用蓄電システムに適用でき、システムにおける蓄電池個数を半減でき、蓄電池のシステム価格を半減できるので、再生エネルギー発電に併設する定置用蓄電システムの普及に大いに貢献できる。結果として再生エネルギーの普及の後押しとなり、脱炭素社会の実現に貢献する。 Since the present invention can store two to several times as many charge carrier ions at the same potential as the current layered metal oxide, it can be applied to a stationary power storage system, the number of storage batteries in the system can be halved, and the system price of the storage battery can be halved. Therefore, it can greatly contribute to the spread of stationary power storage systems that are installed alongside renewable energy power generation. As a result, it will support the spread of renewable energy and contribute to the realization of a decarbonized society.

Claims (1)

  1. 　電荷担体イオンの挿入及び脱離により酸化還元する化合物に囲まれ、その電荷担体イオンが挿入及び脱離することが出来る空隙を有する正極活物質からなることを特徴とする蓄電池。 A storage battery characterized by comprising a positive electrode active material surrounded by a compound that is oxidized and reduced by the insertion and desorption of charge carrier ions and having voids through which the charge carrier ions can be inserted and desorbed.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004253174A (en) * 2003-02-18 2004-09-09 Nichia Chem Ind Ltd Positive pole active material for nonaqueous electrolytic secondary battery
JP2009259605A (en) * 2008-04-17 2009-11-05 Toyota Motor Corp Positive electrode active substance, manufacturing method for same and battery provided with positive electrode active substance
JP2011119092A (en) * 2009-12-02 2011-06-16 Toyota Motor Corp Active material particles, and use of same
WO2012131881A1 (en) * 2011-03-28 2012-10-04 住友金属鉱山株式会社 Nickel-manganese composite hydroxide particles, method for producing same, positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
JP2013118156A (en) * 2011-12-05 2013-06-13 Toyota Motor Corp Lithium ion secondary battery
JP2015043332A (en) * 2014-10-14 2015-03-05 トヨタ自動車株式会社 Lithium secondary battery
JP2017037765A (en) * 2015-08-07 2017-02-16 トヨタ自動車株式会社 Positive electrode material for nonaqueous electrolyte secondary battery and method for producing the same
JP2018045759A (en) * 2016-08-31 2018-03-22 住友化学株式会社 Positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004253174A (en) * 2003-02-18 2004-09-09 Nichia Chem Ind Ltd Positive pole active material for nonaqueous electrolytic secondary battery
JP2009259605A (en) * 2008-04-17 2009-11-05 Toyota Motor Corp Positive electrode active substance, manufacturing method for same and battery provided with positive electrode active substance
JP2011119092A (en) * 2009-12-02 2011-06-16 Toyota Motor Corp Active material particles, and use of same
WO2012131881A1 (en) * 2011-03-28 2012-10-04 住友金属鉱山株式会社 Nickel-manganese composite hydroxide particles, method for producing same, positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery
JP2013118156A (en) * 2011-12-05 2013-06-13 Toyota Motor Corp Lithium ion secondary battery
JP2015043332A (en) * 2014-10-14 2015-03-05 トヨタ自動車株式会社 Lithium secondary battery
JP2017037765A (en) * 2015-08-07 2017-02-16 トヨタ自動車株式会社 Positive electrode material for nonaqueous electrolyte secondary battery and method for producing the same
JP2018045759A (en) * 2016-08-31 2018-03-22 住友化学株式会社 Positive electrode active material for lithium secondary battery, positive electrode for lithium secondary battery, and lithium secondary battery

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