WO2015059779A1 - Matériau d'électrode positive pour des batteries rechargeables lithium-ion et batterie rechargeable lithium-ion - Google Patents

Matériau d'électrode positive pour des batteries rechargeables lithium-ion et batterie rechargeable lithium-ion Download PDF

Info

Publication number
WO2015059779A1
WO2015059779A1 PCT/JP2013/078641 JP2013078641W WO2015059779A1 WO 2015059779 A1 WO2015059779 A1 WO 2015059779A1 JP 2013078641 W JP2013078641 W JP 2013078641W WO 2015059779 A1 WO2015059779 A1 WO 2015059779A1
Authority
WO
WIPO (PCT)
Prior art keywords
positive electrode
ion secondary
lithium ion
secondary battery
electrode material
Prior art date
Application number
PCT/JP2013/078641
Other languages
English (en)
Japanese (ja)
Inventor
小西　宏明
章 軍司
達哉 遠山
孝亮 馮
翔 古月
豊隆 湯浅
小林　満
所　久人
秀一 高野
崇 中林
Original Assignee
株式会社日立製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社日立製作所 filed Critical 株式会社日立製作所
Priority to PCT/JP2013/078641 priority Critical patent/WO2015059779A1/fr
Publication of WO2015059779A1 publication Critical patent/WO2015059779A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • 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 material for a lithium ion secondary battery and a lithium ion secondary battery containing the positive electrode material.
  • Lithium ion secondary batteries have a higher energy density per weight than secondary batteries such as nickel metal hydride batteries and lead batteries. Therefore, application to electric vehicles and power storage systems is expected. However, in order to meet the demands of electric vehicles, it is necessary to further increase the energy density. In order to realize a high energy density of the battery, it is necessary to increase the energy density of the positive electrode and the negative electrode.
  • the layered solid solution represented by Li 2 MnO 3 —LiMO 2 (M is an element such as Ni, Co, Mn, Fe, Ti, Zr, Al, Mg, Cr, V, etc.) has a high capacity, Energy density can be expected.
  • the layered solid solution can also be expressed as a composition Li 1 + x M 1-x O 2 enriched in Li of the layered oxide-based positive electrode active material.
  • Patent Document 1 describes a positive electrode material in which a positive electrode active material composition such as a layered solid solution is coated with a vanadium oxide such as VO x or V 2 O 5 .
  • the layered solid solution can be expected to have a high capacity, there is a problem that a high output cannot be obtained because the resistance is high in a region where the SOC is low.
  • the electron conductivity is improved by coating the positive electrode active material with vanadium oxide, but the resistance is further reduced in a low SOC region for higher output. Is desired.
  • an object of the present invention is to provide a lithium ion secondary battery that maintains a high capacity and has a high output.
  • Positive electrode material for a lithium ion secondary battery the composition formula Li x Ni a Mn 0.8-a -b M b O 2 + ⁇ (0.95 ⁇ x ⁇ 1.2,0.2 ⁇ a ⁇ 0 .4, 0 ⁇ b ⁇ 0.02, ⁇ 1 ⁇ ⁇ ⁇ 1, and M is at least one element selected from Mo, W, Zr, Nb, Ti, Fe, and Cu.
  • Lithium transition metal oxide and lithium vanadium oxide in a mixed state, and the atomic ratio of vanadium to Ni, Mn, and M (V / (Ni + Mn + M)) is 0.01 / 0.8 or more and 0.06 / It is less than 0.8.
  • the layered solid solution positive electrode material of the present invention it is possible to provide a lithium ion secondary battery with high capacity and high output.
  • ⁇ Positive electrode material> When a lithium ion secondary battery is employed in an electric vehicle and a plug-in hybrid vehicle, a high capacity is required, a long traveling distance per charge, a low resistance, and a high output are required.
  • FIG. 1 the result of the DC resistance measurement of a general layered solid solution is shown in FIG. 1, 1 indicates a DC resistance measured while changing the SOC in the discharging direction, and 2 indicates a DC resistance measured while changing the SOC in the charging direction.
  • the direct current resistance is high in a low SOC region.
  • the direct current resistance is measured while changing the SOC (State of Charge) in the charging direction, and the direct current resistance is measured while changing the SOC in the discharging direction.
  • the resistance is different, and particularly when the measurement is performed while changing the SOC in the discharge direction, the resistance is high.
  • the increase in resistance at the end of discharge becomes a big problem. Therefore, in order to improve the output, it is necessary to suppress an increase in resistance in a region where the SOC is low.
  • the range of usable SOC is expanded by reducing the resistance in the low-SOC region.
  • a portion with a high DC resistance value is not used so much because a high output cannot be obtained. Therefore, by reducing the resistance in the low SOC region, the usable SOC range can be expanded and the effective capacity can be improved.
  • the inventors have found that the resistance in a low SOC region can be reduced by using a layered solid solution and a lithium vanadium oxide that absorbs and releases Li at about 3.5 V in the positive electrode material.
  • Lithium vanadium oxide reacts with Li near 3.5V. Therefore, by mixing lithium vanadium oxide into a layered solid solution, lithium vanadium oxide and Li can react in a region where the SOC is low, so that the resistance at the end of discharge can be reduced. As a result, a high output lithium ion secondary battery can be provided.
  • the positive electrode material for a lithium ion secondary battery according to the present invention has a composition formula Li x Ni a Mn 0.8-ab M b O 2 + ⁇ (0.95 ⁇ x ⁇ 1.2, 0.2 ⁇ a ⁇ 0.4). , 0 ⁇ b ⁇ 0.02, ⁇ 1 ⁇ ⁇ ⁇ 1, and M is at least one element selected from Mo, W, Zr, Nb, Ti, Fe, and Cu. It contains transition metal oxide and lithium vanadium oxide in a mixed state.
  • X in the composition formula represents the amount of Li, and if it is less than 0.95, the amount of Li contributing to the reaction is reduced and a high capacity cannot be obtained. On the other hand, if it is larger than 1.2, the crystal lattice becomes unstable and the discharge capacity decreases.
  • a in the composition formula indicates the amount of Ni, and if it is less than 0.2, the amount of Ni contributing to the reaction decreases and a high capacity cannot be obtained. On the other hand, when it is larger than 0.4, the valence of Ni increases, the charge / discharge capacity involving Ni decreases, and a high capacity cannot be obtained.
  • ⁇ in the composition formula represents the amount of oxygen. This value is determined in accordance with the ratio of Li, Ni, and Mn, but may have some non-stoichiometry.
  • M in the composition formula is an additive or impurity that is appropriately added within a range not affecting the present invention, and is at least one element selected from Mo, W, Zr, Nb, Ti, Fe, and Cu.
  • the lithium transition metal oxide is mainly composed of Li, Ni, and Mn, it has an advantage that the cost is lower than that of the positive electrode active material containing a large amount of Co.
  • the atomic ratio of V to Ni, Mn, and M (V / (Ni + Mn + M)) in the positive electrode material is preferably 0.01 / 0.8 or more and less than 0.06 / 0.8.
  • V / (Ni + Mn + M) By setting V / (Ni + Mn + M) to less than 0.06 / 0.8, it is possible to maintain a high capacity and suppress an increase in resistance at the end of discharge.
  • V / (Ni + Mn + M) is 0.06 / 0.8 or more, the amount of lithium that reacts with vanadium increases, the capacity of the positive electrode may decrease, and the resistance may increase.
  • the electrode density can be improved by using a positive electrode material containing a lithium transition metal oxide and a lithium vanadium oxide in a mixed state. This is because the particle size of the lithium vanadium oxide is smaller than that of the lithium transition metal oxide, and particles having different particle sizes can be mixed.
  • primary particles of lithium transition metal oxide and lithium vanadium oxide are preferably mixed. Furthermore, the lithium vanadium oxide is preferably fixed to the primary particle surface of the lithium transition metal oxide. By mixing primary particles of lithium transition metal oxide and lithium vanadium oxide, electronic conduction between the lithium transition metal oxide particles can be enhanced. On the other hand, when secondary particles of lithium transition metal oxide and lithium vanadium oxide are mixed, an electron conduction path between the secondary particles and the conductive material can be constructed, but the lithium transition metal oxide particles inside the secondary particles The electronic conduction between them cannot be increased.
  • the particle state of the positive electrode material can be confirmed by a scanning electron microscope-energy dispersive X-ray analysis (SEM-EDX).
  • the positive electrode material according to the present invention can be produced by a method generally used in the technical field to which the present invention belongs. For example, after preparing a lithium transition metal oxide by mixing a compound containing each of Li, Ni, and Mn at an appropriate ratio and firing, a compound containing V is appropriately added to the obtained lithium transition metal oxide. It can be produced by mixing at a ratio and firing at 850 to 1050 ° C. The composition of the positive electrode material can be appropriately adjusted by changing the ratio of the compound to be mixed. Moreover, you may produce by mixing the compound containing each of Li, Ni, Mn, and V in a suitable ratio, and baking.
  • the lithium transition oxide does not contain Co
  • vanadium is almost dissolved in the lithium transition metal oxide even if it is prepared by mixing and firing the vanadium compound at the stage of mixing the lithium transition metal oxide raw material. This was confirmed by X-ray diffraction measurement.
  • Examples of the compound containing Li include lithium acetate, lithium nitrate, lithium carbonate, lithium hydroxide, and lithium oxide.
  • Examples of the Ni-containing compound include nickel acetate, nickel nitrate, nickel carbonate, nickel sulfate, and nickel hydroxide.
  • Examples of the compound containing Mn include manganese acetate, manganese nitrate, manganese carbonate, manganese sulfate, manganese oxide, and the like.
  • Examples of the compound containing V include vanadium oxide, vanadium nitride, and vanadium boride.
  • composition of the lithium transition metal oxide in the positive electrode material and the amount of V in the positive electrode material can be determined by elemental analysis by, for example, inductively coupled plasma method (ICP).
  • ICP inductively coupled plasma method
  • a lithium ion secondary battery according to the present invention includes the above positive electrode material. By using the above positive electrode material for the positive electrode, a high capacity lithium ion secondary battery can be maintained while maintaining a high capacity.
  • the lithium ion secondary battery according to the present invention can be preferably used for, for example, an electric vehicle.
  • the positive electrode active material occludes and releases lithium ions by charging and discharging. Since all lithium ions released from the positive electrode active material do not return to the positive electrode, the composition of the positive electrode active material after charge / discharge is expected to be different from that before charge / discharge.
  • the layered compound positive electrode active material represented by LiMO 2 has a Li composition ratio of about 0.75 in a fully discharged state (2.5 V) when used in a potential range of 2.5 to 4.3 V. I know that When considered similarly to the layered compound, it is estimated that the amount of Li after charge / discharge of the layered solid solution is also reduced by about 15 to 30% in the full discharge state compared to before charge / discharge.
  • the layered solid solution positive electrode active material is not fully charged (at 2.5 V).
  • the composition is assumed to be Li x Ni a Mn 0.8-a-b M b O 2 + ⁇ (0.80 ⁇ x ⁇ 1.2, 0.2 ⁇ a ⁇ 0.4, ⁇ 1 ⁇ ⁇ ⁇ 1). it can. That is, the lithium transition metal oxide after charge / discharge according to the present invention satisfies 0.090 ⁇ Li / metal element ⁇ 1.5.
  • a lithium ion secondary battery includes a positive electrode including a positive electrode material, a negative electrode including a negative electrode material, a separator, an electrolytic solution, an electrolyte, and the like.
  • the negative electrode material is not particularly limited as long as it is a substance that can occlude and release lithium ions.
  • Substances generally used in lithium ion secondary batteries can be used as the negative electrode material.
  • graphite, a lithium alloy, etc. can be illustrated.
  • separator those generally used in lithium ion secondary batteries can be used.
  • examples thereof include polyolefin microporous films and nonwoven fabrics such as polypropylene, polyethylene, and a copolymer of propylene and ethylene.
  • electrolytic solution and the electrolyte those generally used in lithium ion secondary batteries can be used.
  • diethyl carbonate, dimethyl carbonate, ethylene carbonate, propylene carbonate, vinylene carbonate, methyl acetate, ethyl methyl carbonate, methyl propyl carbonate, dimethoxyethane and the like can be exemplified as the electrolytic solution.
  • a lithium ion secondary battery 12 includes a positive electrode 3 in which a positive electrode active material is applied on both sides of a current collector, a current collector The electrode group which has the negative electrode 4 which apply
  • the negative electrode 6 is electrically connected to the battery can 6 through the negative electrode lead piece 8.
  • a sealing lid 9 is attached to the battery can 6 via a packing 10.
  • the positive electrode 3 is electrically connected to the sealing lid 9 via the positive electrode lead piece 7.
  • the wound body is insulated by the insulating plate 11.
  • the electrode group may not be the wound body shown in FIG. 2, but may be a laminated body in which the positive electrode 3 and the negative electrode 4 are laminated via the separator 5.
  • the positive electrode materials of Examples 1 to 7 and Comparative Example 2 were produced by the following method. Lithium carbonate, nickel carbonate, manganese carbonate, and vanadium oxide were mixed with a ball mill, and the resulting mixture was baked in the atmosphere at 500 ° C. for 12 hours to obtain a lithium transition metal oxide. The obtained lithium transition metal oxide was pelletized and then fired at 850 to 1050 ° C. for 12 hours in the air. The fired pellets were pulverized in an agate mortar and classified with a 45 ⁇ m sieve to obtain a positive electrode material. It was confirmed by X-ray diffraction analysis that the obtained positive electrode material contained a lithium transition metal oxide containing Li, Ni, and Mn and a lithium vanadium oxide containing Li and V.
  • the positive electrode materials of Comparative Examples 1 and 6 to 9 were prepared in the same manner as in Example 1 except that the compound containing the additive element was not mixed.
  • the positive electrode material of Comparative Example 3 was prepared in the same manner as in Example 1 except that vanadium oxide was changed to magnesium oxide. From the X-ray diffraction measurement, it was confirmed that the additive element magnesium was dissolved in the lithium transition metal oxide.
  • the positive electrode material of Comparative Example 4 was prepared in the same manner as in Example 1 except that vanadium oxide was changed to aluminum oxide. By X-ray diffraction measurement, it was confirmed that aluminum as an additive element was dissolved in the lithium transition metal oxide.
  • the positive electrode material of Comparative Example 5 was produced by the following method. Lithium carbonate, nickel carbonate, and manganese carbonate were mixed with a ball mill, and the resulting mixture was fired at 500 ° C. for 12 hours in the air to obtain a lithium transition metal oxide. The obtained lithium transition metal oxide was pelletized and then fired at 850 to 1050 ° C. for 12 hours in the air. The fired pellets were pulverized in an agate mortar and classified with a 45 ⁇ m sieve. Thereafter, a lithium transition metal oxide was added to an aqueous citric acid solution in which vanadium oxide was dissolved, and water was evaporated while stirring at 120 ° C. Then, the positive electrode material which vanadium oxide coat
  • the positive electrode materials used in the examples and comparative examples are shown in Tables 1 to 5.
  • the composition of the lithium transition metal oxide was expressed as Li x Ni a Mn 0.8-a- b MbO 2 + ⁇ .
  • a positive electrode slurry, a conductive agent, and a binder were mixed uniformly to prepare a positive electrode slurry.
  • the positive electrode slurry was applied onto an aluminum current collector foil having a thickness of 20 ⁇ m, dried at 120 ° C., and compression-molded with a press so that the electrode density was 2.2 g / cm 3 to obtain an electrode plate. Thereafter, the electrode plate was punched into a disk shape having a diameter of 15 mm to produce a positive electrode.
  • the negative electrode was produced using metallic lithium.
  • a solution obtained by dissolving LiPF 6 at a concentration of 1.0 mol / L in a mixed solvent of ethylene carbonate and dimethyl carbonate having a volume ratio of 1: 2 was used.
  • the charge / discharge test was performed as follows. The prototype battery was charged and discharged at a current equivalent to 0.05 C with an upper limit voltage of 4.6 V, and discharged at a current equivalent to 0.05 C with a lower limit voltage of 2.5 V. The discharge capacity obtained in the range of 4.6-3.4V was defined as the rated capacity. These discharge capacities are shown in Tables 1 to 5.
  • the DC resistance was determined for the prototype battery as follows. The prototype battery was charged and discharged at a current equivalent to 0.05C with an upper limit voltage of 4.6V, and discharged at a current equivalent to 0.05C with a lower limit voltage of 2.5V. Was the rated capacity. The prototype battery after 2 cycles was charged to 4.6 V, and then 70% of the rated capacity was discharged. Thereafter, a current of 1.2 mA was applied for 10 seconds, and the direct current resistance when the SOC was 30% was measured. A value obtained by dividing the potential difference before applying the current and after applying the current for 10 seconds by the applied current value (1.2 mA) was defined as the DC resistance value. These DC resistances are shown in Tables 1-5.
  • FIG. 3 shows a graph showing the relationship between the SOC and the DC resistance value in Example 1 and Comparative Example 1 when the SOC is changed in the discharge direction.
  • 13 is a plot of the DC resistance value against the SOC of Example 1
  • 14 is a plot of the DC resistance value against the SOC of Comparative Example 1. From FIG. 3, it can be seen that in Example 1 including lithium transition metal oxide and lithium vanadium oxide, the DCR is lower than that in Comparative Example 1 where only the lithium transition metal oxide is present in the SOC range of 20 to 40%. I understood. From this result, it was found that the resistance at the end of discharge can be reduced by using a positive electrode material containing a lithium transition metal oxide and a lithium vanadium oxide in a mixed state. Also, the same graphs as in Example 1 were obtained for Examples 2 to 7. Therefore, by using the positive electrode materials of Examples 1 to 7, the output can be improved while maintaining the high capacity of the lithium ion secondary battery.
  • Comparative Examples 3 and 4 since the added element was Mg or Al not involved in the reaction and was dissolved in the lithium transition metal oxide, the discharge capacity and the direct current resistance were increased. In Comparative Example 5, there was no significant change in both discharge capacity and DC resistance. This is because the positive electrode material of Comparative Example 5 was prepared by mixing vanadium oxide after the synthesis of the lithium transition metal oxide and coating at a low heating temperature, and vanadium oxide was isolated in the positive electrode and did not participate in the reaction. is there.
  • the decrease in discharge capacity was small, and the DC resistance was 40 ⁇ or less. This is because in the positive electrode materials of Examples 1 and 2, the atomic ratio of vanadium to Ni, Mn, and M was 0.02 / 0.8 or less.
  • the atomic ratio of vanadium to Ni, Mn, and M in the positive electrode material including the lithium transition metal oxide and the lithium vanadium oxide is 0.01 / 0.8 or more and less than 0.06 / 0.8.
  • the lithium transition metal oxide represented by the composition formula Li 1.2 Ni 0.2 Mn 0.6 O 2 is also mixed with lithium vanadium oxide to suppress the decrease in discharge capacity to within 2%, and the DC resistance is reduced. It was found that it can be reduced.
  • the lithium transition metal oxide represented by the composition formula Li 1.1 Ni 0.25 Mn 0.55 O 2 is also mixed with lithium vanadium oxide, thereby suppressing the decrease in discharge capacity to within 3% and reducing the DC resistance. It was found that it can be reduced.
  • the lithium transition metal oxide represented by the composition formula LiNi 0.35 Mn 0.45 O 2 can also suppress the decrease in discharge capacity to within 3% and reduce the DC resistance by mixing lithium vanadium oxide. I understood.
  • the lithium transition metal oxide represented by the composition formula Li 0.95 Ni 0.4 Mn 0.4 O 2 is also mixed with lithium vanadium oxide to suppress the decrease in discharge capacity within 3%, and the DC resistance is reduced. Reduced.
  • Examples 1, 4 to 7, Examples 1, 5, and 6 have a high discharge capacity of 175 Ah / kg or more and a low DCR of 40 ⁇ or less. This is because the composition of the lithium transition metal oxide contained in the positive electrode materials of Examples 1, 5, and 6 satisfies 0.25 ⁇ a ⁇ 0.35. By adjusting the composition ratio of Ni and Mn of the lithium transition metal oxide, a positive electrode material having a higher discharge capacity and a lower DCR can be obtained.
  • a positive electrode material of less than 0.06 / 0.8 the decrease in discharge capacity was suppressed to within 5%, and the direct current resistance at the end of discharge was reduced compared to the positive electrode material made of only lithium transition metal oxide. As a result, it is possible to provide a lithium ion secondary battery with high output while maintaining discharge capacity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

La présente invention traite le problème de la fourniture d'un matériau d'électrode positive qui peut obtenir une capacité élevée et présente une faible résistance à l'étape finale de la décharge. Ce problème peut être résolu par un matériau d'électrode positive pour des batteries rechargeables lithium-ion qui est caractérisé par le fait qu'il contient un oxyde de métal de transition lithium représenté par la formule de composition LixNiaMn0,8-a-bMbO2+δ (dans laquelle 0,95 ≤ x ≤ 1,2, 0,2 ≤ a ≤ 0,4, 0 ≤ b < 0,02, -1 ≤ δ ≤ 1 et M représente au moins un élément sélectionné parmi le molybdène (Mo), le tungstène (W), le zirconium (Zr), le niobium (Nb), le titane (Ti), le fer (Fe) et le cuivre (Cu) et un oxyde de lithium et de vanadium dans un état mélangé, et qui est également caractérisé en ce que le rapport atomique entre le vanadium et le nickel (Ni), le manganèse (Mn) et M (V/(Ni + Mn + M)) est égal ou supérieur à 0,01/0,8 mais inférieur à 0,06/0,8.
PCT/JP2013/078641 2013-10-23 2013-10-23 Matériau d'électrode positive pour des batteries rechargeables lithium-ion et batterie rechargeable lithium-ion WO2015059779A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/078641 WO2015059779A1 (fr) 2013-10-23 2013-10-23 Matériau d'électrode positive pour des batteries rechargeables lithium-ion et batterie rechargeable lithium-ion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2013/078641 WO2015059779A1 (fr) 2013-10-23 2013-10-23 Matériau d'électrode positive pour des batteries rechargeables lithium-ion et batterie rechargeable lithium-ion

Publications (1)

Publication Number Publication Date
WO2015059779A1 true WO2015059779A1 (fr) 2015-04-30

Family

ID=52992417

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/078641 WO2015059779A1 (fr) 2013-10-23 2013-10-23 Matériau d'électrode positive pour des batteries rechargeables lithium-ion et batterie rechargeable lithium-ion

Country Status (1)

Country Link
WO (1) WO2015059779A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114975907A (zh) * 2022-03-24 2022-08-30 江苏理工学院 一种硼化钒包覆镍钴锰酸锂正极材料及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003221236A (ja) * 2001-11-22 2003-08-05 Hitachi Maxell Ltd リチウム含有複合酸化物およびそれを用いた非水二次電池
JP2003229128A (ja) * 2002-02-05 2003-08-15 Hitachi Maxell Ltd 非水二次電池及びその製造方法
JP2005235628A (ja) * 2004-02-20 2005-09-02 Nec Corp リチウム二次電池用正極及びリチウム二次電池
JP2008226693A (ja) * 2007-03-14 2008-09-25 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2012089470A (ja) * 2010-09-24 2012-05-10 Toshiba Corp 非水電解質二次電池用正極活物質、非水電解質二次電池、電池パック及び非水電解質二次電池用正極活物質の製造方法
JP2013114847A (ja) * 2011-11-28 2013-06-10 Panasonic Corp リチウムイオン二次電池とその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003221236A (ja) * 2001-11-22 2003-08-05 Hitachi Maxell Ltd リチウム含有複合酸化物およびそれを用いた非水二次電池
JP2003229128A (ja) * 2002-02-05 2003-08-15 Hitachi Maxell Ltd 非水二次電池及びその製造方法
JP2005235628A (ja) * 2004-02-20 2005-09-02 Nec Corp リチウム二次電池用正極及びリチウム二次電池
JP2008226693A (ja) * 2007-03-14 2008-09-25 Matsushita Electric Ind Co Ltd リチウムイオン二次電池
JP2012089470A (ja) * 2010-09-24 2012-05-10 Toshiba Corp 非水電解質二次電池用正極活物質、非水電解質二次電池、電池パック及び非水電解質二次電池用正極活物質の製造方法
JP2013114847A (ja) * 2011-11-28 2013-06-10 Panasonic Corp リチウムイオン二次電池とその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114975907A (zh) * 2022-03-24 2022-08-30 江苏理工学院 一种硼化钒包覆镍钴锰酸锂正极材料及其制备方法

Similar Documents

Publication Publication Date Title
US9601772B2 (en) Cathode active material for a nonaqueous electrolyte secondary battery and manufacturing method thereof, and a nonaqueous electrolyte secondary battery that uses cathode active material
JP5741908B2 (ja) リチウムイオン二次電池用正極活物質
WO2016136212A1 (fr) Accumulateur à électrolyte non aqueux
JP5079291B2 (ja) 非水電解質二次電池
JP2015213038A (ja) 非水電解質二次電池用正極材料および非水電解質二次電池
JP5512056B2 (ja) 非水電解質二次電池およびその製造方法
JP7345125B2 (ja) 非水電解質二次電池用正極活物質の製造方法
WO2016047031A1 (fr) Batterie rechargeable à électrolyte non aqueux
WO2015059778A1 (fr) Matériau actif d&#39;électrode positive pour batteries secondaires au lithium-ion et batterie secondaire au lithium-ion
JP5145994B2 (ja) 非水系電解質二次電池用正極活物質とその製造方法
CN112054190A (zh) 锂二次电池的正极材料和使用该正极材料的锂二次电池
JP6481907B2 (ja) リチウム鉄マンガン系複合酸化物、それを用いたリチウムイオン二次電池用正極活物質、リチウムイオン二次電池用正極、及びリチウムイオン二次電池
WO2017094238A1 (fr) Batterie secondaire à électrolyte non aqueux
JP2018055808A (ja) リチウムイオン二次電池および該リチウムイオン二次電池用の正極活物質
JP6400364B2 (ja) 非水系二次電池用正極活物質及びその製造方法
JP5181455B2 (ja) 非水系電解質二次電池用正極活物質とその製造方法、および、これを用いた非水系電解質二次電池
WO2015132844A1 (fr) Matériau d&#39;électrode positive pour piles rechargeables au lithium ion et pile rechargeable au lithium ion
WO2015059779A1 (fr) Matériau d&#39;électrode positive pour des batteries rechargeables lithium-ion et batterie rechargeable lithium-ion
WO2015004705A1 (fr) Matériau actif d&#39;électrode positive pour des batteries secondaires au lithium-ion
WO2016046868A1 (fr) Matériau actif positif pour batterie rechargeable au lithium-ion, matériau d&#39;électrode positive, et batterie rechargeable au lithium-ion
JP5877898B2 (ja) リチウムイオン二次電池用正極活物質
WO2015019483A1 (fr) Matériau actif d&#39;électrode positive pour batteries secondaires à électrolyte non aqueux, électrode positive pour batteries secondaires à électrolyte non aqueux l&#39;utilisant, et batterie secondaire à électrolyte non aqueux
WO2015019729A1 (fr) Matériau d&#39;électrode positive pour des batteries secondaires au lithium-ion
WO2015037111A1 (fr) Matériau actif d&#39;électrode positive destiné à être utilisé dans des batteries rechargeables au lithium-ion, et batterie rechargeable au lithium-ion utilisant ledit matériau actif d&#39;électrode positive
JP2016058334A (ja) リチウム二次電池用正極材料

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: 13895815

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: 13895815

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP