CN106058214A - Preparation method of graphene interpenetrating manganese-based lamellar lithium battery positive electrode material - Google Patents

Preparation method of graphene interpenetrating manganese-based lamellar lithium battery positive electrode material Download PDF

Info

Publication number
CN106058214A
CN106058214A CN201610636578.5A CN201610636578A CN106058214A CN 106058214 A CN106058214 A CN 106058214A CN 201610636578 A CN201610636578 A CN 201610636578A CN 106058214 A CN106058214 A CN 106058214A
Authority
CN
China
Prior art keywords
lithium battery
graphene
graphite powder
preparation
stirring
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610636578.5A
Other languages
Chinese (zh)
Other versions
CN106058214B (en
Inventor
郭迎庆
盛海丰
王龙
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Zhong can de yuan Energy Technology Co., Ltd.
Original Assignee
郭迎庆
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 郭迎庆 filed Critical 郭迎庆
Priority to CN201610636578.5A priority Critical patent/CN106058214B/en
Publication of CN106058214A publication Critical patent/CN106058214A/en
Application granted granted Critical
Publication of CN106058214B publication Critical patent/CN106058214B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The invention discloses a preparation method of a graphene interpenetrating manganese-based lamellar lithium battery positive electrode material and belongs to the technical field of lithium battery positive electrode material preparation. The preparation method comprises mixing graphite powder and concentrated sulfuric acid, carrying out pumping filtration to obtain pre-oxidized graphite powder, carrying out a stirring reaction process on the pre-oxidized graphite powder, a concentrated sulfuric acid solution, a hydrogen peroxide solution and hydrochloric acid, carrying out centrifugation on the product to obtain precipitates, drying the precipitates, carrying out mixing ball milling on the precipitates, calcined manganese dioxide, lithium hydroxide monohydrate and sodium sulfide, adding deionized water into the mixed powder for a hydro-thermal reaction, and washing and drying the reaction products to obtain the graphene interpenetrating manganese-based lamellar lithium battery positive electrode material. The preparation method has simple processes, low energy consumption and a short period. The product has good low temperature performances and good conductivity and has tap density of 1.9-2.5g/mL.

Description

A kind of Graphene interts the preparation method of manganio layer structure anode material of lithium battery
Technical field
The present invention relates to a kind of Graphene and intert the preparation method of manganio layer structure anode material of lithium battery, belong to lithium electricity Pond positive electrode preparing technical field.
Background technology
The various electric device of mankind's daily use, such as electric automobile, portable type electronic product, it is both needed to use chemistry Power supply.In electrochmical power source used, lithium ion battery has that running voltage height, light weight, volume be little, high-energy-density, memoryless The features such as effect, less, the long circulation life of self discharge and be used widely, the sixth of the twelve Earthly Branches through in portable type electronic product extensively should With, and progressively it is generalized to electric tool and electric vehicle.The performance of lithium ion battery depends primarily on its positive electrode Performance.LiCo02(cobalt acid lithium) is the lithium ion battery of first generation positive electrode, but cobalt resource is limited and to bad environmental, cobalt Acid lithium price is higher, and heat stability and security performance are poor, are unsuitable for the application of electrokinetic cell.It was found that there is Han later The phosphate of olive stone structure, LiFePO4 (LiFeP04), possess the ratio cobalt more preferable safety of acid lithium, the most high temperature resistant, overcharging resisting Electrical property exceeds well over cobalt acid lithium.It is increasingly becoming the dynamic lithium battery positive electrode of current main-stream.But LiFePO4 discharge potential Low, energy density is less, synthetic technological condition is more harsh, the higher Fe in preparation of industrial production cost2+Oxidizable one-tenth Fe3 +, it is difficult to obtain single-phase LiFePO4, purity is low, complicated process of preparation, needs long-time high-temperature calcination, and energy consumption is high, the cycle is long. Although improving ion and electronic conductivity by the doping of lithium position, ferrum position, had by the particle diameter and morphology control improving granule Validity response area, increases the cryogenic property to improve LiFePO4 such as electron conduction by adding extra conductive agent, but The inherent characteristics of LiFePO 4 material, it is extensive that the factors such as its cryogenic property and electric conductivity are poor, and tap density is relatively low limit it Application.
Summary of the invention
The technical problem to be solved: poor for current anode material of lithium battery cryogenic property and electric conductivity, The drawback that tap density is relatively low, it is provided that a kind of graphite powder mixes with concentrated sulphuric acid etc., sucking filtration prepares pre-oxidation graphite powder, then with dense The stirring reaction such as sulfuric acid solution, hydrogenperoxide steam generator, hydrochloric acid, so centrifugal that to precipitate, after drying with burnt manganese dioxide, Dan Shui Lithium hydrate, the mixing and ball milling such as sodium sulfide obtains ball milling material, adds deionized water and carries out hydro-thermal reaction, the dried system of reactant washing Graphene interts the method for manganio layer structure anode material of lithium battery.Preparation process of the present invention is simple, and manufacturing cycle is short, institute Obtaining product cryogenic property and good conductivity, tap density is high.
For solving above-mentioned technical problem, the present invention uses the technical scheme as described below to be:
(1) measuring 33～35mL mass fractions is 98% sulfuric acid solution, under 75～80 DEG C of waters bath with thermostatic control, be separately added into 5.0～ 6.0g graphite powder, 6.2～7.0g potassium peroxydisulfate, 6.2～7.0g phosphorus pentoxide, with 200～300r/min stirrings 4～5h, Mixed liquor, adds mixed liquor in 2～3L deionized waters, and with 200～300nm aperture ultrafilter membranes, it is carried out sucking filtration, obtain filter Cake, after being washed with deionized filter cake 3～5 times, by filter cake natural air drying, obtains pre-oxidation graphite powder；
(2) measuring 30～40mL mass fractions is 98% sulfuric acid solution, under ice-water bath, is separately added into 5～6g in sulfuric acid solution Above-mentioned pre-oxidation graphite powder, 3～4g potassium permanganate, with 100～200r/min stirrings 15～20min, it is again heated to 35～40 DEG C, After continuing stirring 2～3h, stirring mixture is added in 60～70mL deionized waters, stirs 2～3h, be cooled to room temperature, add 180～200mL deionized waters, after stirring, adding 5～6mL mass fractions is 30% hydrogenperoxide steam generator, waits to drip 25 ～after 30min, adding 10～12mL mass fractions is 37% hydrochloric acid, continues stirring 1～2h, stands 20～24h, proceeds to centrifuge In, with 5000～6000r/min centrifugations 10～15min, collect precipitation, and be washed with deionized precipitation 3～5 times, will Precipitation is placed in 60～70 DEG C of drying baker and is dried 3～4h, obtains graphene oxide sheet；
(3) weigh 8.7～13.1g manganese dioxide to be placed in tube furnace, at 800～850 DEG C, calcine 10～12h, furnace cooling To room temperature, take out, it is above-mentioned with 16.8～20.2g monohydrate lithium hydroxides, 1.6～1.9g sodium sulfide, 1.5～2.0g respectively Graphene oxide sheet mixes, and loads in ball grinder, adds 20～30mL dehydrated alcohol, with 120～150r/min in filling simultaneously Ball milling 3～4h, natural air drying, obtain ball milling material；
(4) weigh 5～6g above-mentioned ball milling material, add in 60～72mL deionized waters, with 300～400r/min stirring mixing 1～ After 2h, load reactor, be placed in hydro-thermal reaction 20～24h in 180～200 DEG C of air dry ovens, take out reactant, and spend Ionized water washing reaction thing is neutrality to cleaning mixture, is placed in 80～90 DEG C of air dry ovens by the reactant after washing and is dried 2 ～3h, obtain Graphene and intert manganio layer structure anode material of lithium battery.
The application process of the present invention: the Graphene that the present invention is prepared intert manganio layer structure anode material of lithium battery, Kynoar, acetylene black 8:1:1 in mass ratio mixes, and adds mixture quality 1～2%N-methyl pyrrolidone, Agate mortar grinds to form pastel, is applied on aluminium foil, be dried 10～12h in air atmosphere, then do in 70～80 DEG C of vacuum Dry case is dried 10～12h, prepares a diameter of 8～10mm pole piece, put in the glove box of full argon and be made into battery.Should Material tap density reaches 1.9～2.5g/mL, reaches 131～136mA h at 10C discharge capacity-1, under 0.5C, follow for 80～90 times After ring, its discharge capacitance is more than 99.4%, and cryogenic property is good, is worthy to be popularized and uses.
The present invention is compared with additive method, and Advantageous Effects is:
(1) preparation process of the present invention is simple, and energy consumption is low, and the cycle is short；
(2) products obtained therefrom cryogenic property and good conductivity, tap density reaches 1.9～2.5g/mL.
Detailed description of the invention
First measuring 33～35mL mass fractions is 98% sulfuric acid solution, under 75～80 DEG C of waters bath with thermostatic control, is separately added into 5.0～6.0g graphite powders, 6.2～7.0g potassium peroxydisulfate, 6.2～7.0g phosphorus pentoxide, with 200～300r/min stirring 4～ 5h, obtains mixed liquor, is added in 2～3L deionized waters by mixed liquor, and with 200～300nm aperture ultrafilter membranes, it is carried out sucking filtration, Filter cake, after being washed with deionized filter cake 3～5 times, by filter cake natural air drying, obtain pre-oxidation graphite powder；Measure again 30～ 40mL mass fraction is 98% sulfuric acid solution, under ice-water bath, is separately added into 5～6g above-mentioned pre-oxidation graphite in sulfuric acid solution Powder, 3～4g potassium permanganate, with 100～200r/min stirrings 15～20min, it is again heated to 35～40 DEG C, continues stirring 2～3h After, stirring mixture is added in 60～70mL deionized waters, stirs 2～3h, be cooled to room temperature, add 180～200mL go from Sub-water, after stirring, adding 5～6mL mass fractions is 30% hydrogenperoxide steam generator, after dripping 25～30min, adds 10～12mL mass fractions are 37% hydrochloric acid, continue stirring 1～2h, stand 20～24h, proceed in centrifuge, with 5000～ 6000r/min centrifugation 10～15min, collect precipitation, and be washed with deionized precipitation 3～5 times, precipitation is placed in 60～ 70 DEG C of drying baker are dried 3～4h, obtain graphene oxide sheet；Then weigh 8.7～13.1g manganese dioxide to be placed in tube furnace, At 800～850 DEG C, calcine 10～12h, after cooling to room temperature with the furnace, take out, by its respectively with 16.8～20.2g mono-water hydrogen Lithium oxide, 1.6～the mixing of 1.9g sodium sulfide, 1.5～2.0g above-mentioned graphene oxide sheet, load in ball grinder, simultaneously in filling Add 20～30mL dehydrated alcohol, with 120～150r/min ball millings 3～4h, natural air drying, obtain ball milling material；Finally weigh 5～6g Above-mentioned ball milling material, adds in 60～72mL deionized waters, after 300～400r/min stirring mixing 1～2h, loads reactor, It is placed in hydro-thermal reaction 20～24h in 180～200 DEG C of air dry ovens, takes out reactant, and be washed with deionized reactant It is neutrality to cleaning mixture, the reactant after washing is placed in 80～90 DEG C of air dry ovens and is dried 2～3h, obtain Graphene and intert Manganio layer structure anode material of lithium battery.
Example 1
First measuring 33mL mass fraction is 98% sulfuric acid solution, under 75 DEG C of waters bath with thermostatic control, be separately added into 5.0g graphite powder, 6.2g potassium peroxydisulfate, 6.2g phosphorus pentoxide, stir 4h with 200r/min, obtain mixed liquor, mixed liquor adds 2L deionized water In, and with 200nm aperture ultrafilter membrane, it is carried out sucking filtration, obtain filter cake, after being washed with deionized filter cake 3 times, filter cake is natural Air-dry, obtain pre-oxidation graphite powder；Measuring 30mL mass fraction again is 98% sulfuric acid solution, under ice-water bath, divides in sulfuric acid solution Not Jia Ru 5g above-mentioned pre-oxidation graphite powder, 3g potassium permanganate, with 100r/min stir 15min, be again heated to 35 DEG C, continue stirring After 2h, stirring mixture is added in 60mL deionized water, stirs 2h, be cooled to room temperature, add 180mL deionized water, stirring After Jun Yun, adding 5mL mass fraction is 30% hydrogenperoxide steam generator, after dripping 25～30min, adds 10mL mass fraction It is 37% hydrochloric acid, continues stirring 1h, stand 20h, proceed in centrifuge, with 5000r/min centrifugation 10min, collect precipitation, And it is washed with deionized precipitation 3 times, precipitation is placed in 60 DEG C of drying baker and is dried 3h, obtain graphene oxide sheet；Then weigh 8.7g manganese dioxide is placed in tube furnace, at 800 DEG C, calcine 10h, after cooling to room temperature with the furnace, take out, by its respectively with 16.8g monohydrate lithium hydroxide, 1.6g sodium sulfide, the above-mentioned graphene oxide sheet of 1.5g mix, and load in ball grinder, simultaneously in filling Add 20mL dehydrated alcohol, with 120r/min ball milling 3h, natural air drying, obtain ball milling material；Finally weigh 5g above-mentioned ball milling material, add In 60mL deionized water, after 300r/min stirring mixing 1h, load reactor, be placed in hydro-thermal in 180 DEG C of air dry ovens Reaction 20h, takes out reactant, and to be washed with deionized reactant to cleaning mixture is neutrality, is placed in by the reactant after washing 80 DEG C of air dry ovens are dried 2h, obtain Graphene and intert manganio layer structure anode material of lithium battery.
The application process of the present invention is: the Graphene present invention prepared interts manganio layer structure lithium battery anode material Material, Kynoar, acetylene black 8:1:1 in mass ratio mixes, and adds mixture quality 1%N-methyl pyrrolidone, Agate mortar grinds to form pastel, is applied on aluminium foil, be dried 10h in air atmosphere, more dry in 70 DEG C of vacuum drying ovens Dry 10h, prepares a diameter of 8mm pole piece, puts in the glove box of full argon and be made into battery.This material tap density reaches 1.9g/mL, reaches 131mA h at 10C discharge capacity-1, under 0.5C, after 80 circulations, its discharge capacitance is 99.48%, Cryogenic property is good, is worthy to be popularized and uses.
Example 2
First measuring 34mL mass fraction is 98% sulfuric acid solution, under 78 DEG C of waters bath with thermostatic control, be separately added into 5.5g graphite powder, 6.6g potassium peroxydisulfate, 6.6g phosphorus pentoxide, stir 5h with 250r/min, obtain mixed liquor, mixed liquor adds 3L deionized water In, and with 250nm aperture ultrafilter membrane, it is carried out sucking filtration, obtain filter cake, after being washed with deionized filter cake 4 times, filter cake is natural Air-dry, obtain pre-oxidation graphite powder；Measuring 35mL mass fraction again is 98% sulfuric acid solution, under ice-water bath, divides in sulfuric acid solution Not Jia Ru 6g above-mentioned pre-oxidation graphite powder, 4g potassium permanganate, with 150r/min stir 18min, be again heated to 38 DEG C, continue stirring After 3h, stirring mixture is added in 65mL deionized water, stirs 3h, be cooled to room temperature, add 190mL deionized water, stirring After Jun Yun, adding 6mL mass fraction is 30% hydrogenperoxide steam generator, after dripping 25～30min, adds 11mL mass fraction It is 37% hydrochloric acid, continues stirring 2h, stand 22h, proceed in centrifuge, with 5500r/min centrifugation 13min, collect precipitation, And it is washed with deionized precipitation 4 times, precipitation is placed in 65 DEG C of drying baker and is dried 4h, obtain graphene oxide sheet；Then weigh 11.0g manganese dioxide is placed in tube furnace, at 825 DEG C, calcine 11h, after cooling to room temperature with the furnace, take out, by its respectively with 18.5g monohydrate lithium hydroxide, 1.7g sodium sulfide, the above-mentioned graphene oxide sheet of 1.8g mix, and load in ball grinder, simultaneously in filling Add 25mL dehydrated alcohol, with 135r/min ball milling 4h, natural air drying, obtain ball milling material；Finally weigh 6g above-mentioned ball milling material, add In 66mL deionized water, after 350r/min stirring mixing 2h, load reactor, be placed in hydro-thermal in 190 DEG C of air dry ovens Reaction 22h, takes out reactant, and to be washed with deionized reactant to cleaning mixture is neutrality, is placed in by the reactant after washing 85 DEG C of air dry ovens are dried 3h, obtain Graphene and intert manganio layer structure anode material of lithium battery.
The Graphene present invention prepared interts manganio layer structure anode material of lithium battery, Kynoar, acetylene black 8:1:1 in mass ratio mixes, and adds mixture quality 2%N-methyl pyrrolidone, grinds to form pasty state in agate mortar Thing, is applied on aluminium foil, is dried 11h in air atmosphere, then is dried 11h in 75 DEG C of vacuum drying ovens, prepares a diameter of 9mm pole Sheet, puts in the glove box of full argon and is made into battery.This material tap density reaches 2.3g/mL, at 10C discharge capacity Reach 134mA h-1, under 0.5C, after 85 circulations, its discharge capacitance is 99.56%, and cryogenic property is good, is worthy to be popularized and makes With.
Example 3
First measuring 35mL mass fraction is 98% sulfuric acid solution, under 80 DEG C of waters bath with thermostatic control, be separately added into 6.0g graphite powder, 7.0g potassium peroxydisulfate, 7.0g phosphorus pentoxide, stir 5h with 300r/min, obtain mixed liquor, mixed liquor adds 3L deionized water In, and with 300nm aperture ultrafilter membrane, it is carried out sucking filtration, obtain filter cake, after being washed with deionized filter cake 5 times, filter cake is natural Air-dry, obtain pre-oxidation graphite powder；Measuring 40mL mass fraction again is 98% sulfuric acid solution, under ice-water bath, divides in sulfuric acid solution Not Jia Ru 6g above-mentioned pre-oxidation graphite powder, 4g potassium permanganate, with 200r/min stir 20min, be again heated to 40 DEG C, continue stirring After 3h, stirring mixture is added in 70mL deionized water, stirs 3h, be cooled to room temperature, add 200mL deionized water, stirring After Jun Yun, adding 6mL mass fraction is 30% hydrogenperoxide steam generator, after dripping 25～30min, adds 12mL mass fraction It is 37% hydrochloric acid, continues stirring 2h, stand 24h, proceed in centrifuge, with 6000r/min centrifugation 15min, collect precipitation, And it is washed with deionized precipitation 5 times, precipitation is placed in 70 DEG C of drying baker and is dried 4h, obtain graphene oxide sheet；Then weigh 13.1g manganese dioxide is placed in tube furnace, at 850 DEG C, calcine 12h, after cooling to room temperature with the furnace, take out, by its respectively with 20.2g monohydrate lithium hydroxide, 1.9g sodium sulfide, the above-mentioned graphene oxide sheet of 2.0g mix, and load in ball grinder, simultaneously in filling Add 30mL dehydrated alcohol, with 150r/min ball milling 4h, natural air drying, obtain ball milling material；Finally weigh 6g above-mentioned ball milling material, add In 72mL deionized water, after 400r/min stirring mixing 2h, load reactor, be placed in hydro-thermal in 200 DEG C of air dry ovens Reaction 24h, takes out reactant, and to be washed with deionized reactant to cleaning mixture is neutrality, is placed in by the reactant after washing 90 DEG C of air dry ovens are dried 3h, obtain Graphene and intert manganio layer structure anode material of lithium battery.
The Graphene present invention prepared interts manganio layer structure anode material of lithium battery, Kynoar, acetylene black 8:1:1 in mass ratio mixes, and adds mixture quality 2%N-methyl pyrrolidone, grinds to form pasty state in agate mortar Thing, is applied on aluminium foil, is dried 12h in air atmosphere, then is dried 12h in 80 DEG C of vacuum drying ovens, prepares a diameter of 10mm Pole piece, puts in the glove box of full argon and is made into battery.This material tap density reaches 2.5g/mL, transfers electric capacity at 10C Amount reaches 136mA h-1, under 0.5C, 90 times circulation after its discharge capacitance be 99.72%, cryogenic property is good, be worthy to be popularized with Use.

Claims (1)

1. a Graphene interts the preparation method of manganio layer structure anode material of lithium battery, it is characterised in that specifically prepare step Suddenly it is:
(1) measuring 33～35mL mass fractions is 98% sulfuric acid solution, under 75～80 DEG C of waters bath with thermostatic control, be separately added into 5.0～ 6.0g graphite powder, 6.2～7.0g potassium peroxydisulfate, 6.2～7.0g phosphorus pentoxide, with 200～300r/min stirrings 4～5h, Mixed liquor, adds mixed liquor in 2～3L deionized waters, and with 200～300nm aperture ultrafilter membranes, it is carried out sucking filtration, obtain filter Cake, after being washed with deionized filter cake 3～5 times, by filter cake natural air drying, obtains pre-oxidation graphite powder；
(2) measuring 30～40mL mass fractions is 98% sulfuric acid solution, under ice-water bath, is separately added into 5～6g in sulfuric acid solution Above-mentioned pre-oxidation graphite powder, 3～4g potassium permanganate, with 100～200r/min stirrings 15～20min, it is again heated to 35～40 DEG C, After continuing stirring 2～3h, stirring mixture is added in 60～70mL deionized waters, stirs 2～3h, be cooled to room temperature, add 180～200mL deionized waters, after stirring, adding 5～6mL mass fractions is 30% hydrogenperoxide steam generator, waits to drip 25 ～after 30min, adding 10～12mL mass fractions is 37% hydrochloric acid, continues stirring 1～2h, stands 20～24h, proceeds to centrifuge In, with 5000～6000r/min centrifugations 10～15min, collect precipitation, and be washed with deionized precipitation 3～5 times, will Precipitation is placed in 60～70 DEG C of drying baker and is dried 3～4h, obtains graphene oxide sheet；
(3) weigh 8.7～13.1g manganese dioxide to be placed in tube furnace, at 800～850 DEG C, calcine 10～12h, furnace cooling To room temperature, take out, it is above-mentioned with 16.8～20.2g monohydrate lithium hydroxides, 1.6～1.9g sodium sulfide, 1.5～2.0g respectively Graphene oxide sheet mixes, and loads in ball grinder, adds 20～30mL dehydrated alcohol, with 120～150r/min in filling simultaneously Ball milling 3～4h, natural air drying, obtain ball milling material；
(4) weigh 5～6g above-mentioned ball milling material, add in 60～72mL deionized waters, with 300～400r/min stirring mixing 1～ After 2h, load reactor, be placed in hydro-thermal reaction 20～24h in 180～200 DEG C of air dry ovens, take out reactant, and spend Ionized water washing reaction thing is neutrality to cleaning mixture, is placed in 80～90 DEG C of air dry ovens by the reactant after washing and is dried 2 ～3h, obtain Graphene and intert manganio layer structure anode material of lithium battery.
CN201610636578.5A 2016-08-05 2016-08-05 A kind of graphene interts the preparation method of manganese base layer structure anode material of lithium battery Active CN106058214B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610636578.5A CN106058214B (en) 2016-08-05 2016-08-05 A kind of graphene interts the preparation method of manganese base layer structure anode material of lithium battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610636578.5A CN106058214B (en) 2016-08-05 2016-08-05 A kind of graphene interts the preparation method of manganese base layer structure anode material of lithium battery

Publications (2)

Publication Number Publication Date
CN106058214A true CN106058214A (en) 2016-10-26
CN106058214B CN106058214B (en) 2018-11-23

Family

ID=57481322

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610636578.5A Active CN106058214B (en) 2016-08-05 2016-08-05 A kind of graphene interts the preparation method of manganese base layer structure anode material of lithium battery

Country Status (1)

Country Link
CN (1) CN106058214B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106920948A (en) * 2017-04-21 2017-07-04 常州市好利莱光电科技有限公司 A kind of preparation method of lithium manganate composite anode material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102280617A (en) * 2011-07-06 2011-12-14 中国科学院过程工程研究所 Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof
JP2014505351A (en) * 2010-12-22 2014-02-27 オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド Electrode plate and method for preparing the same, super capacitor and lithium ion battery
CN104393283A (en) * 2014-10-20 2015-03-04 中国工程物理研究院化工材料研究所 Nano crystalline CoO-graphene composite material as well as preparation and application thereof
CN104868105A (en) * 2015-04-15 2015-08-26 南京邮电大学 Preparation method of three-dimensional graphene composite electrode material with high mechanical strength

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014505351A (en) * 2010-12-22 2014-02-27 オーシャンズ キング ライティング サイエンスアンドテクノロジー カンパニー リミテッド Electrode plate and method for preparing the same, super capacitor and lithium ion battery
CN102280617A (en) * 2011-07-06 2011-12-14 中国科学院过程工程研究所 Carbon material modified composite lithium manganese oxide cathode material applied to lithium ion battery and preparation method thereof
CN104393283A (en) * 2014-10-20 2015-03-04 中国工程物理研究院化工材料研究所 Nano crystalline CoO-graphene composite material as well as preparation and application thereof
CN104868105A (en) * 2015-04-15 2015-08-26 南京邮电大学 Preparation method of three-dimensional graphene composite electrode material with high mechanical strength

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106920948A (en) * 2017-04-21 2017-07-04 常州市好利莱光电科技有限公司 A kind of preparation method of lithium manganate composite anode material

Also Published As

Publication number Publication date
CN106058214B (en) 2018-11-23

Similar Documents

Publication Publication Date Title
Jiang et al. Synthesis and performance of a graphene decorated NaTi2 (PO4) 3/C anode for aqueous lithium-ion batteries
Fu et al. Structure and electrochemical properties of nanocarbon-coated Li3V2 (PO4) 3 prepared by sol–gel method
CN101159328A (en) LiFePO4/C nano composite positive pole material and preparation method thereof
CN109728246A (en) A kind of nitrogen-phosphor codoping ordered mesoporous carbon material and its preparation method and application
Yang et al. Facile synthesis of ternary transition metal-organic framework and its stable lithium storage properties
CN105428633A (en) Method for preparing titanium niobate mesoporous microspheres
CN102790216A (en) Supercritical solvent thermal preparation method of cathode material lithium iron phosphate of lithium ion battery
CN106450265A (en) In-situ nitrogen-doped carbon coated lithium titanate composite electrode material and preparation method thereof
CN104852028A (en) Lithium titanate/graphene composite cathode material for lithium ion battery
CN104993116B (en) A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method
Bai et al. LiFePO4/carbon nanowires with 3D nano-network structure as potential high performance cathode for lithium ion batteries
Li et al. Electrochemical performance of Li3V2 (PO4) 3/C prepared with a novel carbon source, EDTA
CN103606672A (en) Rod-shaped nano iron oxide electrode material, and preparation method and application thereof
Huang et al. Design and synthesis of high-rate micron-sized, spherical LiFePO4/C composites containing clusters of nano/microspheres
CN108063228A (en) Composite ferric lithium phosphate material and preparation method thereof, lithium ion battery
CN108539133A (en) Li3V2（PO4）3The preparation method of nanocrystalline/conducting polymer anode material for lithium-ion batteries
CN106876673A (en) The method that one-step method prepares titanium dioxide and the double-deck core shell structure lithium sulfur battery anode material of cladding altogether of Graphene
CN105355892A (en) Preparation method of lithium ion battery cathode
CN103413918B (en) A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium
Huang et al. A simple preparation of rod-like Fe2O3 with superior lithium storage performance
Niu et al. High-rate lithium storage of TiNb2O7/reduced graphene oxide
WO2018095029A1 (en) Method of manufacturing ternary cathode material having graphene core
Liu et al. K-doped V2O5 derived from V-MOF precursor as high-performance cathode for aqueous zinc-ion batteries
CN105958040A (en) Iron trifluoride composite material, preparation method of iron trifluoride composite material, and lithium secondary battery
CN103560245B (en) The vanadium phosphate cathode material of graphene coated and its preparation method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right

Effective date of registration: 20181011

Address after: 264003 8 weft five road, Yantai high tech Zone, Shandong

Applicant after: Beijing Zhong can de yuan Energy Technology Co., Ltd.

Address before: 213164 Room 401, unit 6, Baiyun East Court, Zhong Lou District, Changzhou, Jiangsu.

Applicant before: Guo Yingqing

TA01 Transfer of patent application right
GR01 Patent grant
GR01 Patent grant