WO2019104948A1 - Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery - Google Patents

Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery Download PDF

Info

Publication number
WO2019104948A1
WO2019104948A1 PCT/CN2018/087208 CN2018087208W WO2019104948A1 WO 2019104948 A1 WO2019104948 A1 WO 2019104948A1 CN 2018087208 W CN2018087208 W CN 2018087208W WO 2019104948 A1 WO2019104948 A1 WO 2019104948A1
Authority
WO
WIPO (PCT)
Prior art keywords
molybdenum
limn
doped modified
preparation
manganese
Prior art date
Application number
PCT/CN2018/087208
Other languages
French (fr)
Chinese (zh)
Inventor
何苗
冯叶锋
王成民
Original Assignee
广东工业大学
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 广东工业大学 filed Critical 广东工业大学
Publication of WO2019104948A1 publication Critical patent/WO2019104948A1/en

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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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 invention belongs to the technical field of lithium ion batteries, and in particular relates to a molybdenum doped modified lithium manganate composite material, a preparation method thereof and a lithium ion battery.
  • Lithium-ion batteries are widely used in portable electronic devices such as mobile phones, notebook computers, tablet computers, cameras, etc. due to their high operating voltage, high energy density, long cycle life, low self-discharge rate, low pollution, and no memory effect. in. With the increasing awareness of environmental protection and the rising price of oil, new energy industries such as electric bicycles and electric vehicles have good development prospects. Lithium-ion batteries have become the preferred power battery for electric vehicles because of their many advantages. However, lithium-ion batteries, as power batteries, still face many challenges due to safety performance, energy density, power density, etc., so it is not necessary to develop lithium-ion batteries that meet the requirements of power batteries.
  • Lithium-ion battery cathode material is an important component of lithium-ion battery, which has a great impact on battery performance. Among them, lithium manganate has attracted extensive attention due to its rich resources, low price and non-toxicity. It has great advantages in power battery applications. However, the spinel LiMn 2 O 4 material has a fatal disadvantage, and the capacity decays faster, especially at high temperatures (55 ° C).
  • the object of the present invention is to provide a molybdenum doped modified lithium manganate composite material, a preparation method thereof and a lithium ion battery, and the molybdenum doped modified lithium manganate composite material of the invention has better cycle performance.
  • the invention provides a molybdenum doped modified lithium manganate composite material, which is a molybdenum doped modified lithium manganate surface coated with carbon,
  • the molybdenum doped modified lithium manganate has the chemical formula of Formula I:
  • the mass fraction of carbon is 0.1 to 20%; the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%.
  • the invention provides a preparation method of a molybdenum doped modified lithium manganate composite material, comprising the following steps:
  • the molar ratio of the molybdenum to the manganese in the manganese salt solution is x: (2-x), wherein 0.01 ⁇ x ⁇ 0.1;
  • the mass fraction of carbon is 0.1 to 20%; and the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%.
  • the lithium salt is one or more of lithium hydroxide, lithium carbonate and lithium acetate;
  • the manganese salt is one or more of manganese nitrate, manganese sulfate, and manganese acetate;
  • the organic acid is one or more of citric acid, glucose, sucrose, starch, tartaric acid and glycine;
  • the molar ratio of the organic acid to manganese in the manganese salt is (1 to 5):1.
  • the molybdenum source is one or more of sodium molybdate, ammonia molybdate, magnesium molybdate and potassium molybdate.
  • the temperature of the heating in the step C) is 80 to 150 ° C;
  • the heating time in the step C) is 8 to 20 hours.
  • the temperature in the step C) is 80 to 120 ° C;
  • the drying time in the step C) is 10 to 20 hours.
  • the sintering in the step D) is specifically:
  • the powder material is raised from room temperature to 450-550 ° C at a heating rate of 1 to 5 ° C / min, sintered for 3 to 10 hours; and then heated to 650 to 950 ° C at a heating rate of 1 to 5 ° C / min
  • the material was kept for 8 to 24 hours to obtain a LiMn 2-x Mo x O 4 material.
  • the mass ratio of the carbon source to the LiMn 2-x Mo x O 4 material is (0.1 to 0.5):1.
  • the sintering in the step E) is specifically:
  • the temperature is raised from room temperature to 650-850 ° C at a heating rate of 1 to 5 ° C / min, and the temperature is maintained for 10 to 20 hours to obtain a structure having the structure of Formula I. Molybdenum doped modified lithium manganate composite.
  • the invention provides a lithium ion battery, which is a molybdenum doped modified lithium manganate composite material as described above.
  • LiMn 2 O 4 has a high charge and discharge platform, and the electrolyte is easily oxidized and decomposed at a high voltage.
  • Improper use of the battery, such as overcharge and over discharge will affect the battery performance.
  • the invention provides a molybdenum doped modified lithium manganate composite material, which is a molybdenum doped modified lithium manganate surface coated with carbon, and the molybdenum doped modified lithium manganate has the formula I
  • the invention adopts molybdenum to dope lithium manganate, which can effectively inhibit the Jahn-Teller effect of the spinel structure LiMn 2 O 4 and the dissolution of manganese, thereby improving cycle stability and high temperature performance.
  • the invention also provides a preparation method of a molybdenum doped modified lithium manganate composite material.
  • the invention adds a lithium source, a manganese source, a doping source (molybdenum) according to a certain ratio and adds deionized water for mixing. At a certain temperature, it is slowly evaporated to dryness, and finally a gel is formed. After sintering, a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material can be obtained.
  • the prepared material has excellent electrochemical properties and exhibits excellent cycle stability and high temperature performance. The method is simple in process, low in cost and environmentally friendly, and is suitable for large-scale industrial production.
  • Example 1 is an XRD chart of a LiMn 2-x Mo x O 4 /C composite material in Example 1 of the present invention
  • Example 2 is an SEM image of LiMn 2-x Mo x O 4 /C in Example 1 of the present invention
  • Figure 3 is an SEM image of pure LiMn 2 O 4 in Example 1 of the present invention.
  • Example 4 is a charge-discharge curve of a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material at different rates in Example 1 of the present invention
  • the invention provides a molybdenum doped modified lithium manganate composite material, which is a molybdenum doped modified lithium manganate surface coated with carbon,
  • the molybdenum doped modified lithium manganate has the chemical formula of Formula I:
  • the x is preferably 0.01, 0.05, 0.08 or 0.1; the mass fraction of C is preferably from 1 to 15%, more preferably from 5 to 10%; the mass fraction of the LiMn 2-x Mo x O 4 It is preferably 85 to 99%, more preferably 90 to 95%.
  • the invention also provides a preparation method of a molybdenum doped modified lithium manganate composite material, comprising the following steps:
  • the molar ratio of the molybdenum to the manganese in the manganese salt solution is x: (2-x), wherein 0.01 ⁇ x ⁇ 0.1;
  • the mass fraction of carbon is 0.1 to 20%; and the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%.
  • the lithium salt and the manganese salt are preferably dissolved in deionized water, respectively, and are configured as a lithium salt solution and a manganese salt solution, and then the lithium salt solution and the manganese salt solution are mixed, and then an organic acid is added to obtain a mixed solution.
  • the lithium salt is one or more of lithium hydroxide, lithium carbonate and lithium acetate
  • the manganese salt is one or more of manganese nitrate, manganese sulfate and manganese acetate
  • the organic acid Is one or more of citric acid, glucose, sucrose, starch, tartaric acid and glycine
  • the molar ratio of the organic acid to manganese in the manganese salt is preferably (1 to 5): 1, more preferably (2 to 4) ): 1, specifically, it can be 1:1, 2:1, 3:1, 4:1 or 5:1.
  • the lithium salt and the manganese salt may be added in accordance with the stoichiometric ratio in the formula I.
  • a molybdenum source to the above mixed solution and stirring for 1 to 2 hours to obtain a doping solution, which is preferably one or more of sodium molybdate, ammonia molybdate, magnesium molybdate and potassium molybdate;
  • the molar ratio of the molybdenum source to the manganese in the manganese source is preferably (2-x): x, 0.01 ⁇ x ⁇ 0.1, and the x is preferably 0.01, 0.05, 0.08 or 0.1.
  • the above doping solution is heated, and all the water therein is evaporated to obtain a gel substance, and then the gel substance is dried, and then the dried product is subjected to ball mill crushing to obtain a crushed powder.
  • the heating temperature is preferably 80 to 150 ° C, more preferably 90 to 140 ° C, specifically, 80 ° C, 90 ° C, 115 ° C, 140 ° C or 150 ° C; the heating time It is preferably 8 to 20 hours, more preferably 10 to 17 hours, and specifically, it may be 8 hours, 10 hours, 14 hours, 17 hours or 20 hours.
  • the drying temperature is preferably 80 to 120 ° C, more preferably 90 to 110 ° C, specifically 80 ° C, 90 ° C, 100 ° C, 110 ° C or 120 ° C; the drying time is preferably 10 to 20 The hour is more preferably from 12 to 16 hours, and specifically, it may be 10 hours, 12 hours, 14 hours, 16 hours or 20 hours.
  • the crushed powder material is preferably raised from 25 ° C to 450 to 550 ° C, preferably 470 to 500 ° C in an air atmosphere at 1 to 5 ° C / min, and sintered for 3 to 10 h, preferably 4 to 8 h, more preferably 6.5h; and then raised to 650 to 950 ° C, preferably 700 to 900 ° C, more preferably 750 to 850 ° C, and 8 to 24 hours, preferably 12 to 20 hours, more preferably in an air atmosphere at 1-5 ° C / min. It is 15 to 16 hours; naturally cooled to room temperature to obtain a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material.
  • Mo molybdenum
  • the carbon source is preferably dissolved in deionized water, and then the above LiMn 2-x Mo x O 4 material is added, stirred uniformly, transferred to a ball mill tank, and then deionized water having a solid content of 10 to 60% of the raw material is added.
  • the agate beads were placed in a ball mill to obtain a uniform slurry, which was then dried, ball milled, and sintered.
  • the mass ratio of the carbon source to the LiMn 2-x Mo x O 4 material is preferably (0.1 to 0.5): 1, more preferably (0.2 to 0.4): 1; the agate beads and the ball mill can
  • the mass ratio of the medium material is preferably (1 to 5): 1, more preferably (2 to 4): 1; the rotation speed of the ball mill is preferably 200 to 500 rpm/min, more preferably 300 to 400 rpm/min;
  • the time of ball milling is preferably from 5 to 12 hours, more preferably from 8 to 10 hours.
  • the drying temperature is preferably 80 to 120 ° C, more preferably 90 to 110 ° C, most preferably 100 ° C; and the drying time is preferably 5 to 12 hours, more preferably 8 to 10 hours. .
  • the sintering is preferably carried out in a protective gas atmosphere at a temperature rising rate of 1 to 5 ° C / min from room temperature (ie, 25 ° C) to 650 to 850 ° C, and kept for 10 to 20 hours to obtain molybdenum doping.
  • Modified lithium manganate composite LiMn 2-x Mo x O 4 /C.
  • the sintering temperature is preferably 700 to 800 ° C, specifically 650 ° C, 700 ° C, 750 ° C, 800 ° C or 850 ° C; the holding time is preferably 12 to 18 hours, specifically 10 hours, 12 hours, 15 hours, 18 hours or 20 hours.
  • the protective gas is preferably nitrogen and/or argon.
  • the invention also provides a lithium ion battery, wherein the cathode material of the lithium ion battery is the molybdenum doped modified lithium manganate composite material in the invention.
  • the cathode material of the lithium ion battery is the molybdenum doped modified lithium manganate composite material in the invention.
  • other parts of the lithium ion battery such as a negative electrode, a separator, an electrolyte, and the like, may be those commonly used by those skilled in the art, such as a lithium metal plate for the negative electrode, polypropylene for the separator, and LiPF for the electrolyte. 6 ;
  • Conductive agent is carbon black SuperP, and the binder is PVDF.
  • the prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material is prepared according to the ratio of 90:5:5, and the conductive carbon black SuperP and the binder PVDF are mixed. N-methylpyrrolidone was added and stirred for 12 h. The resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet.
  • the positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material
  • the negative electrode is a lithium metal plate
  • the separator is polypropylene
  • LiPF 6 is electrolysis.
  • the liquid was assembled in a glove box filled with argon to obtain a lithium ion battery.
  • the invention provides a molybdenum doped modified lithium manganate composite material, which is a molybdenum doped modified lithium manganate surface coated with carbon, and the molybdenum doped modified lithium manganate has the formula I
  • the invention adopts molybdenum to dope lithium manganate, which can effectively inhibit the Jahn-Teller effect of the spinel structure LiMn 2 O 4 and the dissolution of manganese, thereby improving cycle stability and high temperature performance.
  • the invention also provides a preparation method of a molybdenum doped modified lithium manganate composite material.
  • the invention adds a lithium source, a manganese source, a doping source (molybdenum) according to a certain ratio and adds deionized water for mixing. At a certain temperature, it is slowly evaporated to dryness, and finally a gel is formed. After sintering, a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material can be obtained.
  • the prepared material has excellent electrochemical properties and exhibits excellent cycle stability and high temperature performance. The method is simple in process, low in cost and environmentally friendly, and is suitable for large-scale industrial production.
  • a molybdenum-doped modified lithium manganate composite material provided by the present invention a preparation method thereof, and a lithium ion battery are described in detail below with reference to the embodiments, but are not to be construed as limiting the scope of the present invention. limited.
  • a certain amount of lithium salt and manganese salt were weighed and dissolved in deionized water according to the molar ratio shown in the chemical formula of the lithium manganate positive electrode material to prepare an aqueous solution having a concentration of 0.05 mol/L, and the above solutions were mixed.
  • An organic acid is added to the above mixed solution in an amount of a molar ratio of the transition metal manganese to the organic acid of 1:1.
  • the molybdenum source was added to the above mixed solution according to a molar ratio of the manganese source to the molybdenum source of 1.99:0.01, and stirred for 1 h.
  • the mixed solution obtained above was stirred at 80 ° C for 8 h until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 80 ° C for 10 h, and then the dried material was taken out for ball milling.
  • crushed powder material was sintered from 25 ° C to 450 ° C for 10 h in an air atmosphere at 1 ° C / min, and then incubated at 1 ° C / min to 650 ° C for 24 h in an air atmosphere, and naturally cooled to room temperature.
  • Fig. 1 is an XRD chart of a LiMn 2-x Mo x O 4 /C composite material in Example 1 of the present invention.
  • the SEM image of the LiMn 2-x Mo x O 4 /C composite material of the molybdenum (Mo) doped modified spinel structure of the present embodiment is compared with the pure LiMn 2 O 4 cathode material obtained in Example 1, as shown in the figure. As shown in 2 to 3, it was found that the microstructure of LiMn 2 O 4 molybdenum (Mo) doping and carbon coating did not change.
  • the prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h.
  • the resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet.
  • the positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material, the negative electrode is a lithium metal plate, the separator is polypropylene, and LiPF 6 is electrolysis.
  • the liquid was assembled in a argon-filled glove box and then tested for electrochemical performance.
  • Example 4 is a charge-discharge curve of a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite prepared in Example 1 at different rates.
  • Mo molybdenum
  • the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite prepared by Example 1 exhibited excellent rate performance, and the discharge ratio was 0.1 C and 5 C ratio.
  • the capacities were 132.3 mAh/g and 113.8 mAh/g, respectively.
  • the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite exhibits good cycle stability, and the capacity retention rate can reach 95.2 at 100 times at 5C rate. %.
  • a certain amount of lithium salt and manganese salt were weighed and dissolved in deionized water according to the molar ratio shown in the chemical formula of the lithium manganate positive electrode material to prepare an aqueous solution having a concentration of 0.5 mol/L, and the above solutions were mixed.
  • An organic acid is added to the above mixed solution in an amount of a molar ratio of transition metal manganese to organic acid of 1:2.
  • the molybdenum source was added to the above mixed solution according to a molar ratio of the manganese source to the molybdenum source of 1.95:0.05, and stirred for 1.2 h.
  • the mixed solution obtained above was stirred at 90 ° C for 10 h until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 90 ° C for 12 h, and then the dried material was taken out for ball milling.
  • crushed powder material was sintered from 25 ° C to 470 ° C for 4 h at 2 ° C / min in an air atmosphere, then raised to 700 ° C for 2 h in an air atmosphere at 2 ° C / min, and naturally cooled to room temperature.
  • the prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h.
  • the resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet.
  • the positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material
  • the negative electrode is a lithium metal plate
  • the separator is polypropylene
  • LiPF 6 is electrolysis.
  • An organic acid is added to the above mixed solution in an amount of a molar ratio of transition metal manganese to organic acid of 1:3.
  • the molybdenum source was added to the above mixed solution according to a molar ratio of manganese source to molybdenum source of 1.95:0.05, and stirred for 1.5 h.
  • the mixed solution obtained above was stirred at 115 ° C for 14 h until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 100 ° C for 15 h, and then the dried material was taken out for ball milling.
  • the crushed powder material is sintered from 25 ° C to 500 ° C for 6.5 h in an air atmosphere at 3 ° C / min, and then raised to 800 ° C for 3 h in an air atmosphere at 3 ° C / min, and naturally cooled to room temperature.
  • a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material was obtained.
  • the prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h.
  • the resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet.
  • the positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material
  • the negative electrode is a lithium metal plate
  • the separator is polypropylene
  • LiPF 6 is electrolysis.
  • An organic acid is added to the above mixed solution in an amount of a molar ratio of the transition metal manganese to the organic acid of 1:4.
  • the molybdenum source was added to the above mixed solution according to a molar ratio of the manganese source to the molybdenum source of 1.92:0.08, and stirred for 1.8 h.
  • the mixed solution obtained above was stirred at 140 ° C for 17 h until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 110 ° C for 16 h, and then the dried material was taken out for ball milling.
  • crushed powder material was sintered from 25 ° C to 560 ° C for 8 h in an air atmosphere at 4 ° C / min, and then raised to 900 ° C for 5 h in an air atmosphere at 4 ° C / min, and naturally cooled to room temperature.
  • the prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h.
  • the resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet.
  • the positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material
  • the negative electrode is a lithium metal plate
  • the separator is polypropylene
  • LiPF 6 is electrolysis.
  • An organic acid is added to the above mixed solution in an amount of a molar ratio of transition metal manganese to organic acid of 1:5.
  • the molybdenum source was added to the above mixed solution according to a molar ratio of manganese source to molybdenum source of 1.9:0.1, and stirred for 2 hours.
  • the mixed solution obtained above was stirred at 150 ° C for 20 hours until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 120 ° C for 20 hours, and then the dried material was taken out for ball milling.
  • crushed powder material was sintered from 25 ° C to 550 ° C for 10 h in an air atmosphere at 5 ° C / min, and then incubated at 5 ° C / min to 950 ° C for 24 h in an air atmosphere, and naturally cooled to room temperature.
  • crushed powder material is heated from 25 ° C to 850 ° C in an inert atmosphere at 10 ° C / min for 10 h, and naturally cooled to room temperature to obtain molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite.
  • the prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h.
  • the resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet.
  • the positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material
  • the negative electrode is a lithium metal plate
  • the separator is polypropylene
  • LiPF 6 is electrolysis.

Abstract

Provided in the present invention is a molybdenum doping-modified lithium manganese oxide composite material, which is molybdenum doping-modified lithium manganese oxide having a surface coated with carbon. The molybdenum doping-modified lithium manganese oxide has a chemical formula represented by formula I: LiMn2-xMoxO4 formula I, wherein 0.01≤x≤0.1; the mass fraction of carbon is 0.1-20％; and the mass fraction of LiMn2-xMoxO4 is 80-99.9％. The present invention uses molybdenum to dope lithium manganese oxide, which may effectively suppress the Jahn-Teller effect in the spinel structure LiMn2O4 as well as the dissolution of manganese, thus improving cycle stability and high temperature performance. Further provided in the present invention is a preparation method for a molybdenum doping-modified lithium manganese oxide composite material. The method has a simple process and costs are low, the method being environmentally friendly and being suitable for large-scale industrial production.

Description

一种钼掺杂改性的锰酸锂复合材料、其制备方法及锂离子电池Lithium doped modified lithium manganate composite material, preparation method thereof and lithium ion battery
本申请要求于2017年11月28日提交中国专利局、申请号为201711214440.7、发明名称为“一种钼掺杂改性的锰酸锂复合材料、其制备方法及锂离子电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims to be filed on November 28, 2017 in China Patent Office, application number 201711214440.7, the invention titled "a molybdenum doped lithium manganate composite material, its preparation method and lithium ion battery" Chinese patent application Priority is hereby incorporated by reference in its entirety.
技术领域Technical field
本发明属于锂离子电池技术领域，尤其涉及一种钼掺杂改性的锰酸锂复合材料、其制备方法及锂离子电池。The invention belongs to the technical field of lithium ion batteries, and in particular relates to a molybdenum doped modified lithium manganate composite material, a preparation method thereof and a lithium ion battery.
背景技术Background technique
锂离子电池由于具有工作电压高、能量密度大、循环寿命长、自放电率低、低污染、无记忆效应等优异性能，被广泛应用于移动电话、笔记本电脑、平板电脑、相机等便携式电子设备中。随着人们环保意识的增强和石油价格的日益高涨，电动自行车、电动汽车等新能源行业具有良好的发展前景，锂离子电池因为具有以上众多优点而成为电动汽车首选的动力电池。然而锂离子电池作为动力电池，由于安全性能、能量密度、功率密度等问题仍然面临着许多的挑战，因此亟须研发出符合动力电池要求的锂离子电池。Lithium-ion batteries are widely used in portable electronic devices such as mobile phones, notebook computers, tablet computers, cameras, etc. due to their high operating voltage, high energy density, long cycle life, low self-discharge rate, low pollution, and no memory effect. in. With the increasing awareness of environmental protection and the rising price of oil, new energy industries such as electric bicycles and electric vehicles have good development prospects. Lithium-ion batteries have become the preferred power battery for electric vehicles because of their many advantages. However, lithium-ion batteries, as power batteries, still face many challenges due to safety performance, energy density, power density, etc., so it is not necessary to develop lithium-ion batteries that meet the requirements of power batteries.
锂离子电池正极材料是锂离子电池的一个重要组成部分，对电池性能影响重大，其中锰酸锂由于具有资源丰富、价格低廉、无毒等优点受到广泛关注，在动力电池中的应用极具优势，但是尖晶石LiMn 2O 4材料有着致命的缺点，容量衰减较快，在高温(55℃)下尤为如此。 Lithium-ion battery cathode material is an important component of lithium-ion battery, which has a great impact on battery performance. Among them, lithium manganate has attracted extensive attention due to its rich resources, low price and non-toxicity. It has great advantages in power battery applications. However, the spinel LiMn 2 O 4 material has a fatal disadvantage, and the capacity decays faster, especially at high temperatures (55 ° C).
发明内容Summary of the invention
本发明的目的在于提供一种钼掺杂改性的锰酸锂复合材料、其制备方法及锂离子电池，本发明中的钼掺杂改性的锰酸锂复合材料具有较好的循环性能。The object of the present invention is to provide a molybdenum doped modified lithium manganate composite material, a preparation method thereof and a lithium ion battery, and the molybdenum doped modified lithium manganate composite material of the invention has better cycle performance.
本发明提供一种钼掺杂改性的锰酸锂复合材料，为表面包覆有碳的钼掺杂改性的锰酸锂，The invention provides a molybdenum doped modified lithium manganate composite material, which is a molybdenum doped modified lithium manganate surface coated with carbon,
所述钼掺杂改性的锰酸锂具有式I所示化学式：The molybdenum doped modified lithium manganate has the chemical formula of Formula I:
LiMn 2-xMo xO 4 式I； LiMn 2-x Mo x O 4 Formula I;
其中，0.01≤x≤0.1；Wherein, 0.01≤x≤0.1;
碳的质量分数为0.1～20％；LiMn 2-xMo xO 4的质量分数为80～99.9％。 The mass fraction of carbon is 0.1 to 20%; the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%.
本发明提供一种钼掺杂改性的锰酸锂复合材料的制备方法，包括以下步骤：The invention provides a preparation method of a molybdenum doped modified lithium manganate composite material, comprising the following steps:
A)将有机酸、锂盐溶液和锰盐溶液混合，得到混合溶液；A) mixing an organic acid, a lithium salt solution and a manganese salt solution to obtain a mixed solution;
B)将钼源加入混合溶液中，得到掺杂溶液；所述钼源中的钼与锰盐溶液中锰的摩尔比为x：(2-x)，其中，0.01≤x≤0.1；B) adding a molybdenum source to the mixed solution to obtain a doping solution; the molar ratio of the molybdenum to the manganese in the manganese salt solution is x: (2-x), wherein 0.01 ≤ x ≤ 0.1;
C)将所述掺杂溶液依次进行加热、干燥和球磨破碎，得到粉体材料；C) sequentially heating, drying and ball milling the doping solution to obtain a powder material;
D)将所述粉体材料进行烧结，得到具有式I所示结构的LiMn 2-xMo xO 4材料； D) sintering the powder material to obtain a LiMn 2-x Mo x O 4 material having the structure of Formula I;
LiMn 2-xMo xO 4/C 式I； LiMn 2-x Mo x O 4 /C Formula I;
其中，0.01≤x≤0.1；Wherein, 0.01≤x≤0.1;
E)将碳源与LiMn 2-xMo xO 4材料混合后进行烧结，得到钼掺杂改性的锰酸锂复合材料； E) mixing the carbon source with the LiMn 2-x Mo x O 4 material and sintering to obtain a molybdenum doped modified lithium manganate composite material;
所述钼掺杂改性的锰酸锂复合材料中，碳的质量分数为0.1～20％；LiMn 2-xMo xO 4的质量分数为80～99.9％。 In the molybdenum doped modified lithium manganate composite, the mass fraction of carbon is 0.1 to 20%; and the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%.
优选的，所述锂盐为氢氧化锂，碳酸锂和醋酸锂中的一种或多种；Preferably, the lithium salt is one or more of lithium hydroxide, lithium carbonate and lithium acetate;
锰盐为硝酸锰、硫酸锰和醋酸锰中的一种或多种；The manganese salt is one or more of manganese nitrate, manganese sulfate, and manganese acetate;
所述有机酸为柠檬酸、葡萄糖、蔗糖、淀粉、酒石酸和甘氨酸中的一种或多种；The organic acid is one or more of citric acid, glucose, sucrose, starch, tartaric acid and glycine;
所述有机酸与锰盐中锰的摩尔比为(1～5)：1。The molar ratio of the organic acid to manganese in the manganese salt is (1 to 5):1.
优选的，所述钼源为钼酸钠、钼酸氨、钼酸镁和钼酸钾中的一种或多种。Preferably, the molybdenum source is one or more of sodium molybdate, ammonia molybdate, magnesium molybdate and potassium molybdate.
优选的，所述步骤C)中加热的温度为80～150℃；Preferably, the temperature of the heating in the step C) is 80 to 150 ° C;
所述步骤C)中加热的时间为8～20小时。The heating time in the step C) is 8 to 20 hours.
优选的，所述步骤C)中干燥的温度为80～120℃；Preferably, the temperature in the step C) is 80 to 120 ° C;
所述步骤C)中干燥的时间为10～20小时。The drying time in the step C) is 10 to 20 hours.
优选的，所述步骤D)中烧结具体为：Preferably, the sintering in the step D) is specifically:
将所述粉体材料以1～5℃/min的升温速率从室温升至450～550℃，烧结3～10小时；然后在以1～5℃/min的升温速率升温至650～950℃保温8～24小时，得到LiMn 2-xMo xO 4材料。 The powder material is raised from room temperature to 450-550 ° C at a heating rate of 1 to 5 ° C / min, sintered for 3 to 10 hours; and then heated to 650 to 950 ° C at a heating rate of 1 to 5 ° C / min The material was kept for 8 to 24 hours to obtain a LiMn 2-x Mo x O 4 material.
优选的，所述碳源与LiMn 2-xMo xO 4材料的质量比为(0.1～0.5)：1。 Preferably, the mass ratio of the carbon source to the LiMn 2-x Mo x O 4 material is (0.1 to 0.5):1.
优选的，所述步骤E)中烧结具体为：Preferably, the sintering in the step E) is specifically:
将碳源与LiMn 2-xMo xO 4材料混合后，以1～5℃/min的升温速率从室温升至650～850℃，保温10～20小时，得到具有式I所示结构的钼掺杂改性的锰酸锂复合材料。 After mixing the carbon source with the LiMn 2-x Mo x O 4 material, the temperature is raised from room temperature to 650-850 ° C at a heating rate of 1 to 5 ° C / min, and the temperature is maintained for 10 to 20 hours to obtain a structure having the structure of Formula I. Molybdenum doped modified lithium manganate composite.
本发明提供一种锂离子电池，所述正极材料为上文所述的钼掺杂改性的锰酸锂复合材料。The invention provides a lithium ion battery, which is a molybdenum doped modified lithium manganate composite material as described above.
申请人经研究发现几种可能的机理导致容量衰减：(1)充放电过程中发生晶格畸变，即Jahn-Teller效应，引起LiMn 2O 4正极材料结构的收缩与膨胀是导致容量衰减的重要原因。(2)锰的溶解也是容量衰减的原因之一。由于尖晶石中含有Mn 3+，在酸性条件下会发生歧化反应：2Mn 3+＝Mn 4++Mn 2+，Mn 2+则可溶解于电解液中，从而造成活性物质的减少，而在高温条件下，歧化反应速度更快。(3)Jahn-Teller效应引起的由立方晶系向四方晶系的结构转变阻碍了锂离子进出的通道，从而使容量衰减。(4)合成材料的结晶度、颗粒大小和形貌、粒径分布等都会影响LiMn 2O 4的电化学性能。(5)LiMn 2O 4具有较高的充放电平台，电解液在高电压下容易氧化分解。(6)不正当使用电池，如过充过放都会影响电池性能。 Applicants have found that several possible mechanisms lead to capacity decay: (1) Lattice distortion occurs during charge and discharge, ie Jahn-Teller effect, causing shrinkage and expansion of LiMn 2 O 4 cathode material structure is important for capacity decay the reason. (2) The dissolution of manganese is also one of the causes of capacity decay. Since the spinel contains Mn 3+ , disproportionation occurs under acidic conditions: 2Mn 3+ = Mn 4+ + Mn 2+ , and Mn 2+ can be dissolved in the electrolyte, resulting in a decrease in active substances. At high temperatures, the disproportionation reaction is faster. (3) The structural transition from the cubic system to the tetragonal system caused by the Jahn-Teller effect hinders the passage of lithium ions into and out, thereby attenuating the capacity. (4) The crystallinity, particle size and morphology, particle size distribution of the synthetic materials all affect the electrochemical performance of LiMn 2 O 4 . (5) LiMn 2 O 4 has a high charge and discharge platform, and the electrolyte is easily oxidized and decomposed at a high voltage. (6) Improper use of the battery, such as overcharge and over discharge will affect the battery performance.
本发明提供了一种钼掺杂改性的锰酸锂复合材料，为表面包覆有碳的钼掺杂改性的锰酸锂，所述钼掺杂改性的锰酸锂具有式I所示化学式：LiMn 2-xMo xO 4式I；其中，0.01≤x≤0.1；碳的质量分数为0.1～20％；LiMn 2-xMo xO 4的质量分数为80～99.9％。本发明采用钼对锰酸锂进行掺杂，能够有效抑制尖晶石结构LiMn 2O 4的Jahn-Teller效应和锰的溶解，从而提高循环稳定性和高温性能。 The invention provides a molybdenum doped modified lithium manganate composite material, which is a molybdenum doped modified lithium manganate surface coated with carbon, and the molybdenum doped modified lithium manganate has the formula I The chemical formula: LiMn 2-x Mo x O 4 formula I; wherein 0.01 ≤ x ≤ 0.1; the mass fraction of carbon is 0.1 to 20%; and the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%. The invention adopts molybdenum to dope lithium manganate, which can effectively inhibit the Jahn-Teller effect of the spinel structure LiMn 2 O 4 and the dissolution of manganese, thereby improving cycle stability and high temperature performance.
本发明还提供了一种钼掺杂改性的锰酸锂复合材料的制备方法，本发明按照一定配比添加锂源，锰源，掺杂源(钼)并且加入去离子水进行混合，在一定温度下，慢慢蒸干，最后形成凝胶，经过烧结后可以得到钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料。所制备出材料具有优异电化学性能，表现出优异循环稳定和高温性能。该方法工艺简单，成本低，环境友好，适用于大规模工业生产。 The invention also provides a preparation method of a molybdenum doped modified lithium manganate composite material. The invention adds a lithium source, a manganese source, a doping source (molybdenum) according to a certain ratio and adds deionized water for mixing. At a certain temperature, it is slowly evaporated to dryness, and finally a gel is formed. After sintering, a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material can be obtained. The prepared material has excellent electrochemical properties and exhibits excellent cycle stability and high temperature performance. The method is simple in process, low in cost and environmentally friendly, and is suitable for large-scale industrial production.
附图说明DRAWINGS
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施 例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below. Obviously, the drawings in the following description are only It is an embodiment of the present invention, and those skilled in the art can obtain other drawings according to the provided drawings without any creative work.
图1为本发明实施例1中LiMn 2-xMo xO 4/C复合材料的XRD图； 1 is an XRD chart of a LiMn 2-x Mo x O 4 /C composite material in Example 1 of the present invention;
图2为本发明实施例1中LiMn 2-xMo xO 4/C的SEM图； 2 is an SEM image of LiMn 2-x Mo x O 4 /C in Example 1 of the present invention;
图3为本发明实施例1中纯LiMn 2O 4的SEM图； Figure 3 is an SEM image of pure LiMn 2 O 4 in Example 1 of the present invention;
图4为本发明实施例1中钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料在不同倍率下充放电曲线； 4 is a charge-discharge curve of a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material at different rates in Example 1 of the present invention;
图5为本发明实施例1中钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料的循环性能曲线。 5 is a cycle performance curve of a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to Embodiment 1 of the present invention.
具体实施方式Detailed ways
本发明提供一种钼掺杂改性的锰酸锂复合材料，为表面包覆有碳的钼掺杂改性的锰酸锂，The invention provides a molybdenum doped modified lithium manganate composite material, which is a molybdenum doped modified lithium manganate surface coated with carbon,
所述钼掺杂改性的锰酸锂具有式I所示化学式：The molybdenum doped modified lithium manganate has the chemical formula of Formula I:
LiMn 2-xMo xO 4 式I； LiMn 2-x Mo x O 4 Formula I;
其中，0.01≤x≤0.1；碳的质量分数为0.1～20％；LiMn 2-xMo xO 4的质量分数为80～99.9％。 Wherein, 0.01 ≤ x ≤ 0.1; the mass fraction of carbon is 0.1 to 20%; and the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%.
在本发明中，所述x优选为0.01、0.05、0.08或0.1；C的质量分数优选为1～15％，更优选为5～10％；所述LiMn 2-xMo xO 4的质量分数优选为85～99％，更优选为90～95％。 In the present invention, the x is preferably 0.01, 0.05, 0.08 or 0.1; the mass fraction of C is preferably from 1 to 15%, more preferably from 5 to 10%; the mass fraction of the LiMn 2-x Mo x O 4 It is preferably 85 to 99%, more preferably 90 to 95%.
本发明还提供了一种钼掺杂改性的锰酸锂复合材料的制备方法，包括以下步骤：The invention also provides a preparation method of a molybdenum doped modified lithium manganate composite material, comprising the following steps:
A)将有机酸、锂盐溶液和锰盐溶液混合，得到混合溶液；A) mixing an organic acid, a lithium salt solution and a manganese salt solution to obtain a mixed solution;
B)将钼源加入混合溶液中，得到掺杂溶液；所述钼源中的钼与锰盐溶液中锰的摩尔比为x：(2-x)，其中，0.01≤x≤0.1；B) adding a molybdenum source to the mixed solution to obtain a doping solution; the molar ratio of the molybdenum to the manganese in the manganese salt solution is x: (2-x), wherein 0.01 ≤ x ≤ 0.1;
C)将所述掺杂溶液依次进行加热、干燥和球磨破碎，得到粉体材料；C) sequentially heating, drying and ball milling the doping solution to obtain a powder material;
D)将所述粉体材料进行烧结，得到具有式I所示结构的LiMn 2-xMo xO 4材料； D) sintering the powder material to obtain a LiMn 2-x Mo x O 4 material having the structure of Formula I;
LiMn 2-xMo xO 4/C 式I； LiMn 2-x Mo x O 4 /C Formula I;
其中，0.01≤x≤0.1；Wherein, 0.01≤x≤0.1;
E)将碳源与LiMn 2-xMo xO 4材料混合后进行烧结，得到钼掺杂改性的锰酸锂复合材料； E) mixing the carbon source with the LiMn 2-x Mo x O 4 material and sintering to obtain a molybdenum doped modified lithium manganate composite material;
所述钼掺杂改性的锰酸锂复合材料中，碳的质量分数为0.1～20％；LiMn 2-xMo xO 4的质量分数为80～99.9％。 In the molybdenum doped modified lithium manganate composite, the mass fraction of carbon is 0.1 to 20%; and the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%.
本发明优选将锂盐和锰盐分别溶于去离子水中，配置成锂盐溶液和锰盐溶液，再将所述锂盐溶液和锰盐溶液混合，然后加入有机酸，得到混合溶液。In the present invention, the lithium salt and the manganese salt are preferably dissolved in deionized water, respectively, and are configured as a lithium salt solution and a manganese salt solution, and then the lithium salt solution and the manganese salt solution are mixed, and then an organic acid is added to obtain a mixed solution.
在本发明中，所述锂盐为氢氧化锂，碳酸锂和醋酸锂中的一种或多种；锰盐为硝酸锰、硫酸锰和醋酸锰中的一种或多种；所述有机酸为柠檬酸、葡萄糖、蔗糖、淀粉、酒石酸和甘氨酸中的一种或多种；所述有机酸与锰盐中锰的摩尔比优选为(1～5)：1，更优选为(2～4)：1，具体的，可以是1:1、2:1、3:1、4:1或5:1。所述锂盐和锰盐按照式I中的化学计量比进行添加即可。In the present invention, the lithium salt is one or more of lithium hydroxide, lithium carbonate and lithium acetate; the manganese salt is one or more of manganese nitrate, manganese sulfate and manganese acetate; the organic acid Is one or more of citric acid, glucose, sucrose, starch, tartaric acid and glycine; the molar ratio of the organic acid to manganese in the manganese salt is preferably (1 to 5): 1, more preferably (2 to 4) ): 1, specifically, it can be 1:1, 2:1, 3:1, 4:1 or 5:1. The lithium salt and the manganese salt may be added in accordance with the stoichiometric ratio in the formula I.
将钼源加入上述混合溶液中，搅拌1～2小时，得到掺杂溶液，所述钼源优选为钼酸钠、钼酸氨、钼酸镁和钼酸钾中的一种或多种；所述钼源与锰源中锰的摩尔比优选为(2-x)：x，0.01≤x≤0.1，所述x优选为0.01、0.05、0.08或0.1。Adding a molybdenum source to the above mixed solution and stirring for 1 to 2 hours to obtain a doping solution, which is preferably one or more of sodium molybdate, ammonia molybdate, magnesium molybdate and potassium molybdate; The molar ratio of the molybdenum source to the manganese in the manganese source is preferably (2-x): x, 0.01 ≤ x ≤ 0.1, and the x is preferably 0.01, 0.05, 0.08 or 0.1.
本发明将上述掺杂溶液加热，将其中的水全部蒸干，得到凝胶物质，然后将所述凝胶物质进行干燥，再将干燥物进行球磨破碎，得到破碎粉体。In the present invention, the above doping solution is heated, and all the water therein is evaporated to obtain a gel substance, and then the gel substance is dried, and then the dried product is subjected to ball mill crushing to obtain a crushed powder.
在本发明中，所述加热的温度优选为80～150℃，更优选为90～140℃，具体的，可以是80℃，90℃，115℃，140℃或150℃；所述加热的时间优选为8～20小时，更优选为10～17小时，具体的，可以是8小时、10小时、14小时、17小时或20小时。所述干燥的温度优选为80～120℃，更优选为90～110℃，具体的，可以是80℃、90℃、100℃、110℃或120℃；所述干燥的时间优选为10～20小时，更优选为12～16小时，具体的，可以是10小时、12小时、14小时、16小时或20小时。In the present invention, the heating temperature is preferably 80 to 150 ° C, more preferably 90 to 140 ° C, specifically, 80 ° C, 90 ° C, 115 ° C, 140 ° C or 150 ° C; the heating time It is preferably 8 to 20 hours, more preferably 10 to 17 hours, and specifically, it may be 8 hours, 10 hours, 14 hours, 17 hours or 20 hours. The drying temperature is preferably 80 to 120 ° C, more preferably 90 to 110 ° C, specifically 80 ° C, 90 ° C, 100 ° C, 110 ° C or 120 ° C; the drying time is preferably 10 to 20 The hour is more preferably from 12 to 16 hours, and specifically, it may be 10 hours, 12 hours, 14 hours, 16 hours or 20 hours.
本发明优选将破碎粉体材料在空气气氛中以1～5℃/min从25℃升到450～550℃、优选为470～500℃，烧结3～10h，优选为4～8h，更优选为6.5h；然后再在空气气氛中以1～5℃/min升到650～950℃，优选为700～900℃，更优选为750～850℃，保温8～24h，优选12～20h，更优选为15～16小时；自然冷 却至室温得到钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料。 In the present invention, the crushed powder material is preferably raised from 25 ° C to 450 to 550 ° C, preferably 470 to 500 ° C in an air atmosphere at 1 to 5 ° C / min, and sintered for 3 to 10 h, preferably 4 to 8 h, more preferably 6.5h; and then raised to 650 to 950 ° C, preferably 700 to 900 ° C, more preferably 750 to 850 ° C, and 8 to 24 hours, preferably 12 to 20 hours, more preferably in an air atmosphere at 1-5 ° C / min. It is 15 to 16 hours; naturally cooled to room temperature to obtain a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material.
本发明优选将碳源溶于去离子水中，然后加入上述LiMn 2-xMo xO 4材料，搅拌均匀后，转移至球磨罐中，然后加入原材料固含量10～60％的去离子水，放入玛瑙珠子，进行球磨，得到均匀的浆料，然后依次进行干燥、球磨破碎和烧结。 In the present invention, the carbon source is preferably dissolved in deionized water, and then the above LiMn 2-x Mo x O 4 material is added, stirred uniformly, transferred to a ball mill tank, and then deionized water having a solid content of 10 to 60% of the raw material is added. The agate beads were placed in a ball mill to obtain a uniform slurry, which was then dried, ball milled, and sintered.
在本发明中，所述碳源与LiMn 2-xMo xO 4材料的质量比优选为(0.1～0.5)：1，更优选为(0.2～0.4)：1；所述玛瑙珠子与球磨罐中物料的质量比优选为(1～5)：1，更优选为(2～4)：1；所述球磨的转速优选为200～500rpm/min，更优选为300～400rpm/min；所述球磨的时间优选为5～12小时，更优选为8～10小时。 In the present invention, the mass ratio of the carbon source to the LiMn 2-x Mo x O 4 material is preferably (0.1 to 0.5): 1, more preferably (0.2 to 0.4): 1; the agate beads and the ball mill can The mass ratio of the medium material is preferably (1 to 5): 1, more preferably (2 to 4): 1; the rotation speed of the ball mill is preferably 200 to 500 rpm/min, more preferably 300 to 400 rpm/min; The time of ball milling is preferably from 5 to 12 hours, more preferably from 8 to 10 hours.
在本发明中，所述干燥的温度优选为80～120℃，更优选为90～110℃，最优选为100℃；所述干燥的时间优选为5～12小时，更优选为8～10小时。In the present invention, the drying temperature is preferably 80 to 120 ° C, more preferably 90 to 110 ° C, most preferably 100 ° C; and the drying time is preferably 5 to 12 hours, more preferably 8 to 10 hours. .
在本发明中，所述烧结优选在保护性气体气氛下，以1～5℃/min的升温速率从室温(即25℃)升至650～850℃，保温10～20小时，得到钼掺杂改性的锰酸锂复合材料(LiMn 2-xMo xO 4/C)。 In the present invention, the sintering is preferably carried out in a protective gas atmosphere at a temperature rising rate of 1 to 5 ° C / min from room temperature (ie, 25 ° C) to 650 to 850 ° C, and kept for 10 to 20 hours to obtain molybdenum doping. Modified lithium manganate composite (LiMn 2-x Mo x O 4 /C).
所述烧结的温度优选为700～800℃，具体的可以是650℃、700℃、750℃、800℃或850℃；所述保温的时间优选为12～18小时，具体的可以是10小时、12小时、15小时、18小时或20小时。The sintering temperature is preferably 700 to 800 ° C, specifically 650 ° C, 700 ° C, 750 ° C, 800 ° C or 850 ° C; the holding time is preferably 12 to 18 hours, specifically 10 hours, 12 hours, 15 hours, 18 hours or 20 hours.
所述保护性气体优选为氮气和/或氩气。The protective gas is preferably nitrogen and/or argon.
本发明还提供了一种锂离子电池，该锂离子电池的正极材料为本发明中的钼掺杂改性的锰酸锂复合材料。在本发明中，所述锂离子电池的其他部分，如负极、隔膜、电解液等部分均可采用本领域技术人员常用的物质，如负极采用金属锂片，隔膜采用聚丙烯，电解液采用LiPF 6；导电剂采用炭黑SuperP，粘结剂采用PVDF。 The invention also provides a lithium ion battery, wherein the cathode material of the lithium ion battery is the molybdenum doped modified lithium manganate composite material in the invention. In the present invention, other parts of the lithium ion battery, such as a negative electrode, a separator, an electrolyte, and the like, may be those commonly used by those skilled in the art, such as a lithium metal plate for the negative electrode, polypropylene for the separator, and LiPF for the electrolyte. 6 ; Conductive agent is carbon black SuperP, and the binder is PVDF.
本发明优选按照90：5：5的比例将制备好的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料，导电炭黑SuperP、粘结剂PVDF混合，加入N-甲基砒咯烷酮，搅拌12h。所得的混合物浆料涂覆在铝箔上，在120℃真空干燥箱里干燥12h得到正极片。正极为钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料和纯LiMn 2O 4正极材料，负极为金属锂片，隔膜为聚丙烯，LiPF 6为电解液，在充满氩气的手套箱中进行电池组装，得到锂离子 电池。 Preferably, the prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material is prepared according to the ratio of 90:5:5, and the conductive carbon black SuperP and the binder PVDF are mixed. N-methylpyrrolidone was added and stirred for 12 h. The resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet. The positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material, the negative electrode is a lithium metal plate, the separator is polypropylene, and LiPF 6 is electrolysis. The liquid was assembled in a glove box filled with argon to obtain a lithium ion battery.
本发明提供了一种钼掺杂改性的锰酸锂复合材料，为表面包覆有碳的钼掺杂改性的锰酸锂，所述钼掺杂改性的锰酸锂具有式I所示化学式：LiMn 2-xMo xO 4式I；其中，0.01≤x≤0.1；碳的质量分数为0.1～20％；LiMn 2-xMo xO 4的质量分数为80～99.9％。本发明采用钼对锰酸锂进行掺杂，能够有效抑制尖晶石结构LiMn 2O 4的Jahn-Teller效应和锰的溶解，从而提高循环稳定性和高温性能。 The invention provides a molybdenum doped modified lithium manganate composite material, which is a molybdenum doped modified lithium manganate surface coated with carbon, and the molybdenum doped modified lithium manganate has the formula I The chemical formula: LiMn 2-x Mo x O 4 formula I; wherein 0.01 ≤ x ≤ 0.1; the mass fraction of carbon is 0.1 to 20%; and the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%. The invention adopts molybdenum to dope lithium manganate, which can effectively inhibit the Jahn-Teller effect of the spinel structure LiMn 2 O 4 and the dissolution of manganese, thereby improving cycle stability and high temperature performance.
本发明还提供了一种钼掺杂改性的锰酸锂复合材料的制备方法，本发明按照一定配比添加锂源，锰源，掺杂源(钼)并且加入去离子水进行混合，在一定温度下，慢慢蒸干，最后形成凝胶，经过烧结后可以得到钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料。所制备出材料具有优异电化学性能，表现出优异循环稳定和高温性能。该方法工艺简单，成本低，环境友好，适用于大规模工业生产。 The invention also provides a preparation method of a molybdenum doped modified lithium manganate composite material. The invention adds a lithium source, a manganese source, a doping source (molybdenum) according to a certain ratio and adds deionized water for mixing. At a certain temperature, it is slowly evaporated to dryness, and finally a gel is formed. After sintering, a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material can be obtained. The prepared material has excellent electrochemical properties and exhibits excellent cycle stability and high temperature performance. The method is simple in process, low in cost and environmentally friendly, and is suitable for large-scale industrial production.
为了进一步说明本发明，以下结合实施例对本发明提供的一种钼掺杂改性的锰酸锂复合材料、其制备方法及锂离子电池进行详细描述，但不能将其理解为对本发明保护范围的限定。In order to further illustrate the present invention, a molybdenum-doped modified lithium manganate composite material provided by the present invention, a preparation method thereof, and a lithium ion battery are described in detail below with reference to the embodiments, but are not to be construed as limiting the scope of the present invention. limited.
实施例1Example 1
1.按照锰酸锂正极材料化学式中所示摩尔比称取一定量锂盐和锰盐溶解在去离子水中，配制成浓度为0.05mol/L的水溶液，并且将以上溶液进行混合。1. A certain amount of lithium salt and manganese salt were weighed and dissolved in deionized water according to the molar ratio shown in the chemical formula of the lithium manganate positive electrode material to prepare an aqueous solution having a concentration of 0.05 mol/L, and the above solutions were mixed.
2.按照过渡金属锰与有机酸摩尔比为1：1的量将有机酸加入到上述混合溶液中。2. An organic acid is added to the above mixed solution in an amount of a molar ratio of the transition metal manganese to the organic acid of 1:1.
3.按照锰源与钼源摩尔比为1.99：0.01将钼源加入上述混合溶液中，进行搅拌1h。3. The molybdenum source was added to the above mixed solution according to a molar ratio of the manganese source to the molybdenum source of 1.99:0.01, and stirred for 1 h.
4.上述获得的混合溶液在80℃下搅拌8h，直至去离子水全部蒸干，得到凝胶物质，然后放到干燥箱里80℃干燥10h后，取出干燥物进行球磨破碎。4. The mixed solution obtained above was stirred at 80 ° C for 8 h until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 80 ° C for 10 h, and then the dried material was taken out for ball milling.
5.最后将破碎粉体材料在空气气氛中以1℃/min从25℃升到450℃烧结10h，然后再在空气气氛中以1℃/min升到650℃保温24h，自然冷却至室温得到钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料。 5. Finally, the crushed powder material was sintered from 25 ° C to 450 ° C for 10 h in an air atmosphere at 1 ° C / min, and then incubated at 1 ° C / min to 650 ° C for 24 h in an air atmosphere, and naturally cooled to room temperature. Molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material.
6.将LiMn 2-xMo xO 4含量10％的碳源溶于去离子水中，加入步骤5所得的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料搅拌，转移到球磨罐里，同 时加入原材料固含量10％的去离子水以及放入玛瑙珠子(物料质量比与珠子为1：1)。在200rpm/min转速下球磨12h，得到均匀浆料物质，然后放到干燥箱里80℃干燥12h后，取出干燥物进行球磨破碎。 6. Dissolve a carbon source having a LiMn 2-x Mo x O 4 content of 10% in deionized water, and add the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material obtained in the step 5 to be stirred. Transfer to the ball mill jar, add 10% deionized water in the raw material and add agate beads (the material mass ratio is 1:1 with the beads). After ball milling for 12 h at 200 rpm/min, a homogeneous slurry material was obtained, which was then dried in a dry box at 80 ° C for 12 h, and the dried material was taken out for ball milling.
7.最后将破碎粉体材料在惰性气氛中以1℃/min从25℃升到650℃保温10h，自然冷却至室温得钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料。 7. Finally, the crushed powder material was heated from 25 ° C to 650 ° C in an inert atmosphere at 10 ° C for 10 h, and naturally cooled to room temperature to obtain a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x . O 4 /C composite.
对实施例1所得的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料与实施例1中所得的纯LiMn 2O 4正极材料的物相结构和微观结构进行表征。如图1所示，图1为本发明实施例1中LiMn 2-xMo xO 4/C复合材料的XRD图。由XRD图所知，钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料保持尖晶石结构，与纯LiMn 2O 4正极材料的衍射峰相似，并且没有出现杂相峰，这说明钼(Mo)掺杂和碳包覆不影响LiFePO 4的物相结构。 The phase structure and microscopic phase of the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite obtained in Example 1 and the pure LiMn 2 O 4 cathode material obtained in Example 1. The structure is characterized. As shown in Fig. 1, Fig. 1 is an XRD chart of a LiMn 2-x Mo x O 4 /C composite material in Example 1 of the present invention. It is known from the XRD pattern that the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite maintains a spinel structure similar to that of a pure LiMn 2 O 4 cathode material, and No heterogeneous peaks appeared, indicating that molybdenum (Mo) doping and carbon coating did not affect the phase structure of LiFePO 4 .
本实施例1钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料与实施例1中所得的纯LiMn 2O 4正极材料的SEM图进行对比，如图2～3所示，发现LiMn 2O 4钼(Mo)掺杂和碳包覆改性后，其微观结构不发生变化。 The SEM image of the LiMn 2-x Mo x O 4 /C composite material of the molybdenum (Mo) doped modified spinel structure of the present embodiment is compared with the pure LiMn 2 O 4 cathode material obtained in Example 1, as shown in the figure. As shown in 2 to 3, it was found that the microstructure of LiMn 2 O 4 molybdenum (Mo) doping and carbon coating did not change.
将实施例1按照90：5：5的比例将制备好的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料，导电炭黑SuperP、粘结剂PVDF混合，加入N-甲基砒咯烷酮，搅拌12h。所得的混合物浆料涂覆在铝箔上，在120℃真空干燥箱里干燥12h得到正极片。正极为钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料和纯LiMn 2O 4正极材料，负极为金属锂片，隔膜为聚丙烯，LiPF 6为电解液，在充满氩气的手套箱中进行电池组装，然后进行电化学性能测试。 The prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h. The resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet. The positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material, the negative electrode is a lithium metal plate, the separator is polypropylene, and LiPF 6 is electrolysis. The liquid was assembled in a argon-filled glove box and then tested for electrochemical performance.
图4为实施例1制得的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料在不同倍率下充放电曲线。由图4可知，由实施例1制得钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料表现出优异倍率性能，在0.1C和5C倍率下放电比容量分别为132.3mAh/g和113.8mAh/g。 4 is a charge-discharge curve of a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite prepared in Example 1 at different rates. As can be seen from FIG. 4, the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite prepared by Example 1 exhibited excellent rate performance, and the discharge ratio was 0.1 C and 5 C ratio. The capacities were 132.3 mAh/g and 113.8 mAh/g, respectively.
通过图5能够看出钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料表现较好循环稳定性，在5C倍率下循环100次容量保持率可以达到95.2％。 It can be seen from Fig. 5 that the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite exhibits good cycle stability, and the capacity retention rate can reach 95.2 at 100 times at 5C rate. %.
实施例2Example 2
1.按照锰酸锂正极材料化学式中所示摩尔比称取一定量锂盐和锰盐溶解在去离子水中，配制成浓度为0.5mol/L的水溶液，并且将以上溶液进行混合。1. A certain amount of lithium salt and manganese salt were weighed and dissolved in deionized water according to the molar ratio shown in the chemical formula of the lithium manganate positive electrode material to prepare an aqueous solution having a concentration of 0.5 mol/L, and the above solutions were mixed.
2.按照过渡金属锰与有机酸摩尔比为1：2的量将有机酸加入到上述混合溶液中。2. An organic acid is added to the above mixed solution in an amount of a molar ratio of transition metal manganese to organic acid of 1:2.
3.按照锰源与钼源摩尔比为1.95：0.05将钼源加入上述混合溶液中，进行搅拌1.2h。3. The molybdenum source was added to the above mixed solution according to a molar ratio of the manganese source to the molybdenum source of 1.95:0.05, and stirred for 1.2 h.
4.上述获得的混合溶液在90℃下搅拌10h，直至去离子水全部蒸干，得到凝胶物质，然后放到干燥箱里90℃干燥12h后，取出干燥物进行球磨破碎。4. The mixed solution obtained above was stirred at 90 ° C for 10 h until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 90 ° C for 12 h, and then the dried material was taken out for ball milling.
5.最后将破碎粉体材料在空气气氛中以2℃/min从25℃升到470℃烧结4h，然后再在空气气氛中以2℃/min升到700℃保温10h，自然冷却至室温得到钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料。 5. Finally, the crushed powder material was sintered from 25 ° C to 470 ° C for 4 h at 2 ° C / min in an air atmosphere, then raised to 700 ° C for 2 h in an air atmosphere at 2 ° C / min, and naturally cooled to room temperature. Molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material.
6.将LiMn 2-xMo xO 4含量20％的碳源溶于去离子水中，加入步骤5所得的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料搅拌，转移到球磨罐里，同时加入原材料固含量20％的去离子水以及放入玛瑙珠子(物料质量比与珠子为1：2)。在300rpm/min转速下球磨7h，得到均匀浆料物质，然后放到干燥箱里90℃干燥8h后，取出干燥物进行球磨破碎。 6. Dissolve a carbon source having a LiMn 2-x Mo x O 4 content of 20% in deionized water, and add the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material obtained in step 5. Transfer to a ball mill jar, add 20% deionized water in the raw material and add agate beads (material mass ratio and beads are 1:2). After ball milling for 7 h at 300 rpm/min, a homogeneous slurry material was obtained, which was then dried in a dry box at 90 ° C for 8 h, and the dried material was taken out for ball milling.
7.最后将破碎粉体材料在惰性气氛中以2℃/min从25℃升到700℃保温12h，自然冷却至室温得钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料。 7. Finally, the crushed powder material was heated from 25 ° C to 700 ° C in an inert atmosphere at 12 ° C for 12 h, and naturally cooled to room temperature to obtain a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x . O 4 /C composite.
将实施例2按照90：5：5的比例将制备好的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料，导电炭黑SuperP、粘结剂PVDF混合，加入N-甲基砒咯烷酮，搅拌12h。所得的混合物浆料涂覆在铝箔上，在120℃真空干燥箱里干燥12h得到正极片。正极为钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料和纯LiMn 2O 4正极材料，负极为金属锂片，隔膜为聚丙烯，LiPF 6为电解液，在充满氩气的手套箱中进行电池组装。在25℃下，在3.0～4.3V间进行电化学性能测试，结果表明钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料具有较高比容量，循环稳定，优异倍率性能，表现出优异电化学性能。 The prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h. The resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet. The positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material, the negative electrode is a lithium metal plate, the separator is polypropylene, and LiPF 6 is electrolysis. Liquid, battery assembly in an argon-filled glove box. Electrochemical performance tests were carried out at 25 ° C between 3.0 and 4.3 V. The results show that the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite has a high specific capacity and circulation. Stable, excellent rate performance, showing excellent electrochemical performance.
实施例3Example 3
1.按照锰酸锂正极材料化学式中所示摩尔比称取一定量锂盐和锰盐溶解在去离子水中，配制成浓度为1.53mol/L的水溶液，并且将以上溶液进行混合。1. A certain amount of lithium salt and manganese salt were weighed and dissolved in deionized water according to the molar ratio shown in the chemical formula of the lithium manganate cathode material to prepare an aqueous solution having a concentration of 1.53 mol/L, and the above solutions were mixed.
2.按照过渡金属锰与有机酸摩尔比为1：3的量将有机酸加入到上述混合溶液中。2. An organic acid is added to the above mixed solution in an amount of a molar ratio of transition metal manganese to organic acid of 1:3.
3.按照锰源与钼源摩尔比为1.95：0.05将钼源加入上述混合溶液中，进行搅拌1.5h。3. The molybdenum source was added to the above mixed solution according to a molar ratio of manganese source to molybdenum source of 1.95:0.05, and stirred for 1.5 h.
4.上述获得的混合溶液在115℃下搅拌14h，直至去离子水全部蒸干，得到凝胶物质，然后放到干燥箱里100℃干燥15h后，取出干燥物进行球磨破碎。4. The mixed solution obtained above was stirred at 115 ° C for 14 h until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 100 ° C for 15 h, and then the dried material was taken out for ball milling.
5.最后将破碎粉体材料在空气气氛中以3℃/min从25℃升到500℃烧结6.5h，然后再在空气气氛中以3℃/min升到800℃保温16h，自然冷却至室温得到钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料。 5. Finally, the crushed powder material is sintered from 25 ° C to 500 ° C for 6.5 h in an air atmosphere at 3 ° C / min, and then raised to 800 ° C for 3 h in an air atmosphere at 3 ° C / min, and naturally cooled to room temperature. A molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material was obtained.
6.将LiMn 2-xMo xO 4含量30％的碳源溶于去离子水中，加入步骤5所得的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料搅拌，转移到球磨罐里，同时加入原材料固含量35％的去离子水以及放入玛瑙珠子(物料质量比与珠子为1：3)。在350rpm/min转速下球磨8.5h，得到均匀浆料物质，然后放到干燥箱里100℃干燥8.5h后，取出干燥物进行球磨破碎。 6. Dissolve a carbon source having a LiMn 2-x Mo x O 4 content of 30% in deionized water, and add the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material obtained in the step 5 to be stirred. Transfer to a ball mill jar, add 35% deionized water in the raw material and add agate beads (material mass ratio and beads are 1:3). After ball milling at 350 rpm/min for 8.5 h, a homogeneous slurry material was obtained, which was then dried in a dry box at 100 ° C for 8.5 h, and then the dried material was taken out for ball milling.
7.最后将破碎粉体材料在惰性气氛中以3℃/min从25℃升到750℃保温15h，自然冷却至室温得钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料。 7. Finally, the crushed powder material was heated from 25 ° C to 750 ° C in an inert atmosphere for 15 h at 3 ° C / min, and naturally cooled to room temperature to obtain a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x . O 4 /C composite.
将实施例3按照90：5：5的比例将制备好的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料，导电炭黑SuperP、粘结剂PVDF混合，加入N-甲基砒咯烷酮，搅拌12h。所得的混合物浆料涂覆在铝箔上，在120℃真空干燥箱里干燥12h得到正极片。正极为钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料和纯LiMn 2O 4正极材料，负极为金属锂片，隔膜为聚丙烯，LiPF 6为电解液，在充满氩气的手套箱中进行电池组装。在25℃下，在3.0～4.3V间进行电化学性能测试，结果表明钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料具有较高比容量，循环稳定，优异倍率性能，表现出优异电化学性能。 The prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h. The resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet. The positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material, the negative electrode is a lithium metal plate, the separator is polypropylene, and LiPF 6 is electrolysis. Liquid, battery assembly in an argon-filled glove box. Electrochemical performance tests were carried out at 25 ° C between 3.0 and 4.3 V. The results show that the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite has a high specific capacity and circulation. Stable, excellent rate performance, showing excellent electrochemical performance.
实施例4Example 4
1.按照锰酸锂正极材料化学式中所示摩尔比称取一定量锂盐和锰盐溶解在去离子水中，配制成浓度为2mol/L的水溶液，并且将以上溶液进行混合。1. A certain amount of lithium salt and manganese salt were weighed and dissolved in deionized water according to the molar ratio shown in the chemical formula of the lithium manganate positive electrode material to prepare an aqueous solution having a concentration of 2 mol/L, and the above solutions were mixed.
2.按照过渡金属锰与有机酸摩尔比为1：4的量将有机酸加入到上述混合溶液中。2. An organic acid is added to the above mixed solution in an amount of a molar ratio of the transition metal manganese to the organic acid of 1:4.
3.按照锰源与钼源摩尔比为1.92：0.08将钼源加入上述混合溶液中，进行搅拌1.8h。3. The molybdenum source was added to the above mixed solution according to a molar ratio of the manganese source to the molybdenum source of 1.92:0.08, and stirred for 1.8 h.
4.上述获得的混合溶液在140℃下搅拌17h，直至去离子水全部蒸干，得到凝胶物质，然后放到干燥箱里110℃干燥16h后，取出干燥物进行球磨破碎。4. The mixed solution obtained above was stirred at 140 ° C for 17 h until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 110 ° C for 16 h, and then the dried material was taken out for ball milling.
5.最后将破碎粉体材料在空气气氛中以4℃/min从25℃升到560℃烧结8h，然后再在空气气氛中以4℃/min升到900℃保温15h，自然冷却至室温得到钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料。 5. Finally, the crushed powder material was sintered from 25 ° C to 560 ° C for 8 h in an air atmosphere at 4 ° C / min, and then raised to 900 ° C for 5 h in an air atmosphere at 4 ° C / min, and naturally cooled to room temperature. Molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material.
6.将LiMn 2-xMo xO 4含量40％的碳源溶于去离子水中，加入步骤5所得的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料搅拌，转移到球磨罐里，同时加入原材料固含量50％的去离子水以及放入玛瑙珠子(物料质量比与珠子为1：4)。在400rpm/min转速下球磨10h，得到均匀浆料物质，然后放到干燥箱里110℃干燥10h后，取出干燥物进行球磨破碎。 6. Dissolve a carbon source having a LiMn 2-x Mo x O 4 content of 40% in deionized water, and add the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material obtained in the step 5 to be stirred. Transfer to a ball-milling jar, add deionized water with 50% solids content of the raw material and add agate beads (material mass ratio to bead 1:4). After ball milling at 400 rpm/min for 10 h, a homogeneous slurry material was obtained, which was then dried in a dry box at 110 ° C for 10 h, and then the dried material was taken out for ball milling.
7.最后将破碎粉体材料在惰性气氛中以4℃/min从25℃升到800℃保温18h，自然冷却至室温得钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料。 7. Finally, the crushed powder material was heated from 25 ° C to 800 ° C in an inert atmosphere at 18 ° C for 18 h, and naturally cooled to room temperature to obtain a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x . O 4 /C composite.
将实施例4按照90：5：5的比例将制备好的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料，导电炭黑SuperP、粘结剂PVDF混合，加入N-甲基砒咯烷酮，搅拌12h。所得的混合物浆料涂覆在铝箔上，在120℃真空干燥箱里干燥12h得到正极片。正极为钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料和纯LiMn 2O 4正极材料，负极为金属锂片，隔膜为聚丙烯，LiPF 6为电解液，在充满氩气的手套箱中进行电池组装。在25℃下，在3.0～4.3V间进行电化学性能测试，结果表明钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料具有较高比容量，循环稳定，优异倍率性能，表现出 优异电化学性能。 The prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h. The resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet. The positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material, the negative electrode is a lithium metal plate, the separator is polypropylene, and LiPF 6 is electrolysis. Liquid, battery assembly in an argon-filled glove box. Electrochemical performance tests were carried out at 25 ° C between 3.0 and 4.3 V. The results show that the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite has a high specific capacity and circulation. Stable, excellent rate performance, showing excellent electrochemical performance.
实施例5Example 5
1.按照锰酸锂正极材料化学式中所示摩尔比称取一定量锂盐和锰盐溶解在去离子水中，配制成浓度为3mol/L的水溶液，并且将以上溶液进行混合。1. A certain amount of lithium salt and manganese salt were weighed and dissolved in deionized water according to the molar ratio shown in the chemical formula of the lithium manganate positive electrode material to prepare an aqueous solution having a concentration of 3 mol/L, and the above solutions were mixed.
2.按照过渡金属锰与有机酸摩尔比为1：5的量将有机酸加入到上述混合溶液中。2. An organic acid is added to the above mixed solution in an amount of a molar ratio of transition metal manganese to organic acid of 1:5.
3.按照锰源与钼源摩尔比为1.9：0.1将钼源加入上述混合溶液中，进行搅拌2h。3. The molybdenum source was added to the above mixed solution according to a molar ratio of manganese source to molybdenum source of 1.9:0.1, and stirred for 2 hours.
4.上述获得的混合溶液在150℃下搅拌20h，直至去离子水全部蒸干，得到凝胶物质，然后放到干燥箱里120℃干燥20h后，取出干燥物进行球磨破碎。4. The mixed solution obtained above was stirred at 150 ° C for 20 hours until all of the deionized water was evaporated to dryness to obtain a gel material, which was then dried in a dry box at 120 ° C for 20 hours, and then the dried material was taken out for ball milling.
5.最后将破碎粉体材料在空气气氛中以5℃/min从25℃升到550℃烧结10h，然后再在空气气氛中以5℃/min升到950℃保温24h，自然冷却至室温得到钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料。 5. Finally, the crushed powder material was sintered from 25 ° C to 550 ° C for 10 h in an air atmosphere at 5 ° C / min, and then incubated at 5 ° C / min to 950 ° C for 24 h in an air atmosphere, and naturally cooled to room temperature. Molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material.
6.将LiMn 2-xMo xO 4含量50％的碳源溶于去离子水中，加入步骤5所得的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4材料搅拌，转移到球磨罐里，同时加入原材料固含量60％的去离子水以及放入玛瑙珠子(物料质量比与珠子为1：5)。在500rpm/min转速下球磨12h，得到均匀浆料物质，然后放到干燥箱里120℃干燥12h后，取出干燥物进行球磨破碎。 6. Dissolve a carbon source having a LiMn 2-x Mo x O 4 content of 50% in deionized water, and add the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 material obtained in step 5. Transfer to a ball mill jar, add deionized water with 60% solids content of the raw material and add agate beads (material mass ratio to bead 1:5). After ball milling for 12 h at 500 rpm/min, a homogeneous slurry material was obtained, which was then dried in a dry box at 120 ° C for 12 h, and the dried material was taken out for ball milling.
7.最后将破碎粉体材料在惰性气氛中以5℃/min从25℃升到850℃保温10h，自然冷却至室温得钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料。 7. Finally, the crushed powder material is heated from 25 ° C to 850 ° C in an inert atmosphere at 10 ° C / min for 10 h, and naturally cooled to room temperature to obtain molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite.
将实施例5按照90：5：5的比例将制备好的钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料，导电炭黑SuperP、粘结剂PVDF混合，加入N-甲基砒咯烷酮，搅拌12h。所得的混合物浆料涂覆在铝箔上，在120℃真空干燥箱里干燥12h得到正极片。正极为钼(Mo)掺杂改性尖晶石结构LiMn 2-xMo xO 4/C复合材料和纯LiMn 2O 4正极材料，负极为金属锂片，隔膜为聚丙烯，LiPF 6为电解液，在充满氩气的手套箱中进行电池组装。在25℃下，在3.0～4.3V间进行电化学性能测试，结果表明钼(Mo)掺杂改性尖晶石结构 LiMn 2-xMo xO 4/C复合材料具有较高比容量，循环稳定，优异倍率性能，表现出优异电化学性能。 The prepared molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material according to the ratio of 90:5:5, conductive carbon black SuperP, binder PVDF Mix, add N-methylpyrrolidone, and stir for 12 h. The resulting mixture slurry was coated on an aluminum foil and dried in a vacuum oven at 120 ° C for 12 hours to obtain a positive electrode sheet. The positive electrode is a molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite material and a pure LiMn 2 O 4 positive electrode material, the negative electrode is a lithium metal plate, the separator is polypropylene, and LiPF 6 is electrolysis. Liquid, battery assembly in an argon-filled glove box. Electrochemical performance tests were carried out at 25 ° C between 3.0 and 4.3 V. The results show that the molybdenum (Mo) doped modified spinel structure LiMn 2-x Mo x O 4 /C composite has a high specific capacity and circulation. Stable, excellent rate performance, showing excellent electrochemical performance.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above description is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can also make several improvements and retouchings without departing from the principles of the present invention. It should be considered as the scope of protection of the present invention.

Claims (10)

  1. 一种钼掺杂改性的锰酸锂复合材料，为表面包覆有碳的钼掺杂改性的锰酸锂，A molybdenum doped modified lithium manganate composite material, which is a molybdenum doped modified lithium manganate coated with carbon,
    所述钼掺杂改性的锰酸锂具有式I所示化学式：The molybdenum doped modified lithium manganate has the chemical formula of Formula I:
    LiMn 2-xMo xO 4    式I； LiMn 2-x Mo x O 4 Formula I;
    其中，0.01≤x≤0.1；Wherein, 0.01≤x≤0.1;
    碳的质量分数为0.1～20％；LiMn 2-xMo xO 4的质量分数为80～99.9％。 The mass fraction of carbon is 0.1 to 20%; the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%.
  2. 一种钼掺杂改性的锰酸锂复合材料的制备方法，包括以下步骤：A preparation method of a molybdenum doped modified lithium manganate composite material, comprising the following steps:
    A)将有机酸、锂盐溶液和锰盐溶液混合，得到混合溶液；A) mixing an organic acid, a lithium salt solution and a manganese salt solution to obtain a mixed solution;
    B)将钼源加入混合溶液中，得到掺杂溶液；所述钼源中的钼与锰盐溶液中锰的摩尔比为x：(2-x)，其中，0.01≤x≤0.1；B) adding a molybdenum source to the mixed solution to obtain a doping solution; the molar ratio of the molybdenum to the manganese in the manganese salt solution is x: (2-x), wherein 0.01 ≤ x ≤ 0.1;
    C)将所述掺杂溶液依次进行加热、干燥和球磨破碎，得到粉体材料；C) sequentially heating, drying and ball milling the doping solution to obtain a powder material;
    D)将所述粉体材料进行烧结，得到具有式I所示结构的LiMn 2-xMo xO 4材料； D) sintering the powder material to obtain a LiMn 2-x Mo x O 4 material having the structure of Formula I;
    LiMn 2-xMo xO 4/C       式I； LiMn 2-x Mo x O 4 /C Formula I;
    其中，0.01≤x≤0.1；Wherein, 0.01≤x≤0.1;
    E)将碳源与LiMn 2-xMo xO 4材料混合后进行烧结，得到钼掺杂改性的锰酸锂复合材料； E) mixing the carbon source with the LiMn 2-x Mo x O 4 material and sintering to obtain a molybdenum doped modified lithium manganate composite material;
    所述钼掺杂改性的锰酸锂复合材料中，碳的质量分数为0.1～20％；LiMn 2-xMo xO 4的质量分数为80～99.9％。 In the molybdenum doped modified lithium manganate composite, the mass fraction of carbon is 0.1 to 20%; and the mass fraction of LiMn 2-x Mo x O 4 is 80 to 99.9%.
  3. 根据权利要求2所述的制备方法，其特征在于，所述锂盐为氢氧化锂，碳酸锂和醋酸锂中的一种或多种；The preparation method according to claim 2, wherein the lithium salt is one or more of lithium hydroxide, lithium carbonate and lithium acetate;
    锰盐为硝酸锰、硫酸锰和醋酸锰中的一种或多种；The manganese salt is one or more of manganese nitrate, manganese sulfate, and manganese acetate;
    所述有机酸为柠檬酸、葡萄糖、蔗糖、淀粉、酒石酸和甘氨酸中的一种或多种；The organic acid is one or more of citric acid, glucose, sucrose, starch, tartaric acid and glycine;
    所述有机酸与锰盐中锰的摩尔比为(1～5)：1。The molar ratio of the organic acid to manganese in the manganese salt is (1 to 5):1.
  4. 根据权利要求2所述的制备方法，其特征在于，所述钼源为钼酸钠、钼酸氨、钼酸镁和钼酸钾中的一种或多种。The preparation method according to claim 2, wherein the molybdenum source is one or more of sodium molybdate, ammonia molybdate, magnesium molybdate and potassium molybdate.
  5. 根据权利要求2所述的制备方法，其特征在于，所述步骤C)中加热的温度为80～150℃；The preparation method according to claim 2, wherein the temperature in the step C) is 80 to 150 ° C;
    所述步骤C)中加热的时间为8～20小时。The heating time in the step C) is 8 to 20 hours.
  6. 根据权利要求2所述的制备方法，其特征在于，所述步骤C)中干燥的温度为80～120℃；The preparation method according to claim 2, wherein the drying temperature in the step C) is 80 to 120 ° C;
    所述步骤C)中干燥的时间为10～20小时。The drying time in the step C) is 10 to 20 hours.
  7. 根据权利要求2所述的制备方法，其特征在于，所述步骤D)中烧结具体为：The preparation method according to claim 2, wherein the sintering in the step D) is specifically:
    将所述粉体材料以1～5℃/min的升温速率从室温升至450～550℃，烧结3～10小时；然后在以1～5℃/min的升温速率升温至650～950℃保温8～24小时，得到LiMn 2-xMo xO 4材料。 The powder material is raised from room temperature to 450-550 ° C at a heating rate of 1 to 5 ° C / min, sintered for 3 to 10 hours; and then heated to 650 to 950 ° C at a heating rate of 1 to 5 ° C / min The material was kept for 8 to 24 hours to obtain a LiMn 2-x Mo x O 4 material.
  8. 根据权利要求2所述的制备方法，其特征在于，所述碳源与LiMn 2-xMo xO 4材料的质量比为(0.1～0.5)：1。 The preparation method according to claim 2, wherein a mass ratio of the carbon source to the LiMn 2-x Mo x O 4 material is (0.1 to 0.5):1.
  9. 根据权利要求2所述的制备方法，其特征在于，所述步骤E)中烧结具体为：The preparation method according to claim 2, wherein the sintering in the step E) is specifically:
    将碳源与LiMn 2-xMo xO 4材料混合后，以1～5℃/min的升温速率从室温升至650～850℃，保温10～20小时，得到具有式I所示结构的钼掺杂改性的锰酸锂复合材料。 After mixing the carbon source with the LiMn 2-x Mo x O 4 material, the temperature is raised from room temperature to 650-850 ° C at a heating rate of 1 to 5 ° C / min, and the temperature is maintained for 10 to 20 hours to obtain a structure having the structure of Formula I. Molybdenum doped modified lithium manganate composite.
  10. 一种锂离子电池，其特征在于，所述正极材料为权利要求1中的钼掺杂改性的锰酸锂负极材料或权利要求2～9任意一项所述的制备方法制得的钼掺杂改性的锰酸锂负极材料。A lithium ion battery, characterized in that the positive electrode material is the molybdenum doped modified lithium manganate negative electrode material according to claim 1 or the molybdenum doping prepared by the preparation method according to any one of claims 2 to 9. Hybrid modified lithium manganate anode material.
PCT/CN2018/087208 2017-11-28 2018-05-17 Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery WO2019104948A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201711214440.7A CN107994220A (en) 2017-11-28 2017-11-28 LiMn2O4 composite material, its preparation method and the lithium ion battery that a kind of molybdenum doping is modified
CN201711214440.7 2017-11-28

Publications (1)

Publication Number Publication Date
WO2019104948A1 true WO2019104948A1 (en) 2019-06-06

Family

ID=62033658

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/087208 WO2019104948A1 (en) 2017-11-28 2018-05-17 Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery

Country Status (2)

Country Link
CN (1) CN107994220A (en)
WO (1) WO2019104948A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107994220A (en) * 2017-11-28 2018-05-04 广东工业大学 LiMn2O4 composite material, its preparation method and the lithium ion battery that a kind of molybdenum doping is modified
CN112939091B (en) * 2021-02-01 2022-10-21 山东海科创新研究院有限公司 Double-modified lithium manganate material and preparation method thereof
CN115528228B (en) * 2022-09-28 2023-04-14 安徽博石高科新材料股份有限公司 Lithium molybdate coated modified lithium manganate material and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0973217A2 (en) * 1998-07-13 2000-01-19 Ngk Insulators, Ltd. Lithium transition metal compound for lithium secondary battery
CN101913655A (en) * 2010-09-10 2010-12-15 河南联合新能源有限公司 Method for preparing lithium manganate cathode material by microwave sintering
CN102259931A (en) * 2011-05-24 2011-11-30 姚金翰 Method for preparing lithium manganese oxide battery material
CN103730654A (en) * 2014-01-18 2014-04-16 南通瑞翔新材料有限公司 High-capacity high-stability lithium manganate positive electrode material and preparation method thereof
CN104961161A (en) * 2015-05-25 2015-10-07 华南理工大学 Highly-stable lithium manganate positive electrode material and preparation method thereof
CN107994220A (en) * 2017-11-28 2018-05-04 广东工业大学 LiMn2O4 composite material, its preparation method and the lithium ion battery that a kind of molybdenum doping is modified

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130107092A (en) * 2012-03-21 2013-10-01 삼성정밀화학 주식회사 Positive electrode for lithium ion secondary battery and lithium ion secondary battery including the same
CN103746105B (en) * 2013-11-28 2015-11-11 福建师范大学 The method of spinel type lithium-rich lithium manganate cathode material is prepared by doping molybdenum ion
CN105789568B (en) * 2014-12-16 2019-05-07 绍兴文理学院 A kind of doping element sulphur richness lithium lithium manganate material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0973217A2 (en) * 1998-07-13 2000-01-19 Ngk Insulators, Ltd. Lithium transition metal compound for lithium secondary battery
CN101913655A (en) * 2010-09-10 2010-12-15 河南联合新能源有限公司 Method for preparing lithium manganate cathode material by microwave sintering
CN102259931A (en) * 2011-05-24 2011-11-30 姚金翰 Method for preparing lithium manganese oxide battery material
CN103730654A (en) * 2014-01-18 2014-04-16 南通瑞翔新材料有限公司 High-capacity high-stability lithium manganate positive electrode material and preparation method thereof
CN104961161A (en) * 2015-05-25 2015-10-07 华南理工大学 Highly-stable lithium manganate positive electrode material and preparation method thereof
CN107994220A (en) * 2017-11-28 2018-05-04 广东工业大学 LiMn2O4 composite material, its preparation method and the lithium ion battery that a kind of molybdenum doping is modified

Also Published As

Publication number Publication date
CN107994220A (en) 2018-05-04

Similar Documents

Publication Publication Date Title
US11855285B2 (en) Full-gradient nickel cobalt manganese positive electrode material, ruthenium oxide coated material and preparation method thereof
CN107403913B (en) Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof
CN107275606B (en) Carbon-coated spinel lithium manganate nanocomposite and preparation method and application thereof
CN103904321B (en) The high-temperature solid phase preparation method of lithium ion battery negative material LiMn2O4
CN110931797A (en) High-nickel positive electrode material with composite coating layer and preparation method thereof
CN110112388B (en) Porous tungsten trioxide coated modified positive electrode material and preparation method thereof
CN107369815B (en) Lithium ion secondary battery composite positive electrode material and preparation method thereof
CN107069001B (en) Honeycomb zinc sulfide/carbon composite negative electrode material and preparation method thereof
CN103151528A (en) Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material
CN103794779A (en) Aluminum oxide coated lithium manganese oxide spinel positive electrode material as well as preparation method thereof
WO2016202162A1 (en) Method for synthesizing lithium-ion negative-electrode material li4ti5o12/c
CN110233261B (en) Preparation method of single crystal ternary lithium battery positive electrode material and lithium ion battery
CN106784790A (en) A kind of preparation method of nickle cobalt lithium manganate tertiary cathode material
CN103219507A (en) Composite material with tubular structure as well as preparation method and application thereof
CN108091854A (en) A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof
WO2019104948A1 (en) Molybdenum doping-modified lithium manganese oxide composite material, preparation method therefor and lithium ion battery
CN107946564B (en) Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof
WO2019080310A1 (en) Molybdenum-doped lithium-rich manganese-based cathode material and preparation method therefor
CN105514375A (en) Carbon-coated Na0.55 Mn2O4.1.5H2O nanocomposite and preparation method thereof
CN114229921A (en) Al2O3-ZrO2Coated lithium-rich manganese-based positive electrode material and preparation method thereof
CN108598405B (en) Preparation method of three-dimensional graphene tin oxide carbon composite negative electrode material
CN113644274A (en) O2 type lithium ion battery anode material and preparation method and application thereof
CN104425810A (en) Modified lithium nickel manganese oxygen material, preparation method of modified lithium nickel manganese oxygen material, and lithium ion battery
CN103187566A (en) Tubular lithium-rich anode material, preparation method and application thereof
CN109461917B (en) Preparation method of lanthanum zirconate in-situ coated high-nickel ternary cathode material

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: 18883087

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: 18883087

Country of ref document: EP

Kind code of ref document: A1