CN108400320A - A method of in spinel nickel manganate cathode material for lithium surface sulfide - Google Patents
A method of in spinel nickel manganate cathode material for lithium surface sulfide Download PDFInfo
- Publication number
- CN108400320A CN108400320A CN201810179127.2A CN201810179127A CN108400320A CN 108400320 A CN108400320 A CN 108400320A CN 201810179127 A CN201810179127 A CN 201810179127A CN 108400320 A CN108400320 A CN 108400320A
- Authority
- CN
- China
- Prior art keywords
- nickel
- powder
- cathode material
- manganate cathode
- hours
- 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
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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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 present invention relates to a kind of methods in spinel nickel manganate cathode material for lithium surface sulfide.The compound of soluble Li, Ni, Mn are first dissolved in deionized water by this method in molar ratio, obtain mixed solution, it adds metal ion chelation agent and obtains gel liquid, dry, grind into powder, nickel lithium manganate cathode material powder is obtained through calcining, then the powder is scattered in absolute ethyl alcohol, 3 aminopropyl triethoxysilanes are added, it washs, centrifuge after reaction, the nickel lithium manganate cathode material powder of surface active is obtained after dry.It takes above-mentioned positive electrode powder and thioacetamide to be scattered in absolute ethyl alcohol, adjusts pH value 7.5 ~ 8.5, wash, centrifuge after reaction, be sintered after dry, obtain the nickel lithium manganate cathode material of surface sulfide.The present invention effectively changes the surface component of nickel lithium manganate cathode material using sulfuration process, improves the cycle performance and high rate performance of nickel lithium manganate cathode material, is easy to industrially practice.
Description
Technical field：
The present invention relates to a kind of methods in spinel nickel manganate cathode material for lithium surface sulfide, belong to lithium ion battery
Technical field of material.
Technical background
Lithium ion battery be it is of new generation practical can charge and discharge electrical storage cell, have operating voltage is high, energy density is high,
Have extended cycle life, the advantages that memory-less effect and self discharge are small, have been widely used for portable electronic product, electric tool,
The numerous areas such as the new energy vehicles, military equipment, aerospace and accumulation power supply system, are considered as 21 century to the people
The new high-tech product that life, national economy and social development are of great significance.Electric vehicle, intelligent grid and big rule
Mould energy storage field flourishes so that the lithium ion battery with high working voltage and high-energy density is increasingly becoming industry
The research hotspot in field.The chemical property of lithium ion battery depends primarily on electrode used therein active material and electrolyte
Structure and performance, wherein anode material for lithium-ion batteries directly determines the energy density of battery, power density, using the longevity
The performances such as life and security feature, are the key influence factors of performance of lithium ion battery.
Spinel-type nickel ion doped is a kind of positive electrode with three-dimensional lithium ion tunnel, and reversible specific capacity is
146.7mAh/g, removal lithium embedded voltage platform are 4.7V vs Li/Li+Left and right has higher energy density, it is considered to be under
Most competitive one of positive electrode, causes vast section in generation high-energy density/high power density lithium ion battery
Grind the highest attention and research extensively of worker.But under high removal lithium embedded voltage, electrolyte is easy on nickel ion doped surface
It decomposes, reduces the transmitting medium amount in battery；Meanwhile the Mn in nickel ion doped3+Disproportionated reaction easily occurs and generates Mn2+And Mn4 +, wherein Mn2+It is soluble in electrolyte so that the Mn in nickel ion doped3+A large amount of losses, thereby reduce the capacity of battery.Surface
Modification is to improve the important channel of nickel ion doped chemical property.By surface modification layer of substance, can alleviate in electrolyte
Corrosion of the hydrofluoric acid to nickel ion doped, inhibit the dissolving of manganese, and then improve cycle performance of battery.Poly- α-the cyano of Liu et al.
Ethyl acrylate coats LiNi0.5Mn1.5O4Particle surface, capacity is kept after spinel anode material 100 recycles after surface modification
Rate is 92% and material capacity conservation rate that surface is unmodified is only 74.7%.Peng et al. utilizes teos hydrolysis technique
In LiNi0.5Mn1.5O4Particle surface modifies silica, and the capacity retention ratio of material significantly improves after modifying silica.Peng
Et al. by simple butter of tin ethanol solution method in LiNi0.5Mn1.5O4It is 2wt% that particle surface, which deposited mass fraction,
SnO2, under the conditions of 2C current charging and dischargings, the capacity retention ratio of battery is up to 57% after 500 cycles.Deng et al. utilizes molten
Glue-gel method is in LiNi0.5Mn1.5O4Particle surface Li2SiO3Capacity retention ratio is significantly improved, as (1-x)
LiNi0.5Mn1.5O4·x Li2SiO3Middle Li2SiO3When covering amount x=0.10, the initial discharge specific capacity of positive electrode up to~
150.3 mAh/g.Although many experiments report confirms that surface modification significantly improves the electrification of nickel lithium manganate cathode material
Performance is learned, but in place of reported most surfaces method of modifying all comes with some shortcomings, as finishing coat cannot sink well
Adhesive attraction power of the product between positive electrode surface, finishing coat and positive electrode surface is not strong, this is undoubtedly increased just
Interface resistance between the material of pole generates negative effect to the improvement of positive electrode chemical property.
Invention content
In order to solve the above problem in the presence of nickel lithium manganate cathode material surface modification common process, the present invention carries
For a kind of method in the vulcanization of spinel anode material surface in situ, positive electrode particle surface not only can be uniformly modified, but also can
To enhance the adhesive attraction power between finishing coat and positive electrode surface, the high nickel ion doped of chemical property is prepared
Positive electrode.
To achieve the purpose of the present invention the technical solution adopted is that：
1, the compound of soluble Li, Ni, Mn are pressed into (1+x)：0.5：1.5 molar ratios are dissolved in deionized water, are sufficiently stirred
Clear mixed solution is obtained, wherein 0≤x≤0.1；
2, metal ion chelating drug is added in mixed solution and stirs 6~10 hours, uses ammonium hydroxide or ethylenediamine tune later
The pH value of above-mentioned solution is saved, pH range is 6~7.
3, the mixed solution that step 2 obtains is positioned in the water-bath that temperature is 80~90 DEG C and continues to stir and flows back,
Stirring obtains gel liquid after 8~24 hours.
Solubility Li compounds of the present invention are one kind in lithium acetate, lithium nitrate and lithium sulfate.
Solubility Ni compounds of the present invention are one kind in nickel acetate, nickel nitrate and nickel sulfate.
Soluble M n compounds of the present invention are one kind in manganese acetate, manganese nitrate and manganese sulfate.
Metal ion chelating drug of the present invention is the one kind for referring to oxalic acid, citric acid, tartaric acid, metal ion chelating
The dosage of agent is 2.0~4.0 times of all metal ions substance mole summation in mixed solution.
4, gel liquid is placed in air dry oven or Muffle furnace under air atmosphere and is dried, it then will be after drying
The puffy substance obtained is ground, and obtains Gel Precursor powder.The drying temperature is 250~280 DEG C of sections
Some temperature, drying time be 8~24 hours.
5, the Gel Precursor powder being collected into is placed in Muffle furnace or atmosphere furnace, is divided under air or oxygen atmosphere
Two benches are calcined, and are cooled to room temperature with stove after calcining, are obtained nickel lithium manganate cathode material.
The two benches calcining, first stage：Calcination temperature is 450 ~ 550 DEG C, and the liter of calcination temperature is raised to from room temperature
Warm rate is 1~5 DEG C/min, and calcination time is 3~8 hours；Second stage：Calcination temperature is 850~950 DEG C, from the first rank
The heating rate that section calcining temperature is raised to second stage calcination temperature is 2~5 DEG C/min, and calcination time is 9~20 hours.
6, it weighs the nickel lithium manganate cathode material of certain mass and is scattered in absolute ethyl alcohol, ultrasonic vibration 2~6 hours
3- aminopropyl triethoxysilanes are added afterwards, wherein 0.03 gram of nickel ion doped needs 0.5~3ml 3- aminopropyl-triethoxy silicon
Alkane.After reaction 5~15 hours, is washed, centrifuged with absolute ethyl alcohol, be then dried to obtain the nickel ion doped powder of surface active
End.
7, the nickel ion doped powder and thioacetamide for weighing the surface active of certain mass are scattered in absolute ethyl alcohol,
Ammonium hydroxide or ethylenediamine is used to adjust the pH value of solution later, pH range is 7.5~8.5.After reaction 3~6 hours, with anhydrous second
Alcohol washing centrifuges, and being then dried to obtain adsorption has the nickel ion doped powder of sulphion.
8, the nickel ion doped powder of sulphion is placed in atmosphere furnace adsorption, in argon gas or argon hydrogen mixed atmosphere
It being sintered under enclosing, sintering temperature is 300~500 DEG C, and the heating rate that sintering temperature is raised to from room temperature is 1~5 DEG C/min,
Sintering time is 8~15 hours；It is cooled to room temperature with stove after sintering, obtains the nickel lithium manganate cathode material of surface sulfide.
The present invention effectively changes the surface component of nickel lithium manganate cathode material using sulfuration process, improves nickel manganese
The cycle performance and high rate performance of sour lithium anode material.And this method technical process is simple, equipment requirement is low, at low cost, is easy to
Industrially practice.
Description of the drawings
Fig. 1 is LiNi prepared by the embodiment of the present invention 10.5Mn1.5O4With the LiNi of surface sulfide0.5Mn1.5O4The X of sample is penetrated
Ray diffraction diagram is composed.
Fig. 2 is the electron scanning micrograph of sample prepared by the embodiment of the present invention 1：(a) LiNi0.5Mn1.5O4；(b)
The LiNi of surface sulfide0.5Mn1.5O4。
Fig. 3 is (a) cycle performance curve of sample prepared by the embodiment of the present invention 1；(b) high rate performance.
Fig. 4 is the electron scanning micrograph of sample prepared by the embodiment of the present invention 2：(a) LiNi0.5Mn1.5O4；(b)
The LiNi of surface sulfide0.5Mn1.5O4。
Fig. 5 is the cycle performance curve of sample prepared by the embodiment of the present invention 2：(a)LiNi0.5Mn1.5O4；(b) surface sulphur
The LiNi of change0.5Mn1.5O4。
Specific implementation mode
With reference to the accompanying drawings and embodiments, the present invention will be further described.
Embodiment 1
2.724 grams of nickel acetates are weighed, 7.348 grams of manganese acetates and 2.300 grams of lithium acetates are dissolved in 400ml deionized waters
In, 13.142 grams of tartaric acid are added after persistently stirring 30 minutes at room temperature, instills ammonium hydroxide in stirring, adjusts the PH of solution
The pH value of value, solution is controlled 6.8 or so, is then stirred continuously until to obtain gel liquid under 90 DEG C of water-baths.
Gel liquid is placed in drying 10 hours in the air dry oven that temperature is 280 DEG C, will then be obtained after drying
Puffy substance be ground, obtain Gel Precursor powder.
The Gel Precursor powder being collected into is placed in Muffle furnace, is calcined under air atmosphere：First with 3 DEG C/s's
Heating rate rises to 500 DEG C from room temperature, and 900 DEG C are risen to again with 3 DEG C/min of heating rate after being sintered 5 hours at 500 DEG C,
900 DEG C are calcined 12 hours.It is naturally cooling to room temperature with stove after calcining, powder, grinding and sieving is taken out and obtains
LiNi0.5Mn1.5O4Positive electrode.
Weigh 0.027 gram of LiNi0.5Mn1.5O4Powder is simultaneously scattered in 200ml absolute ethyl alcohols, and ultrasonic vibration adds after 3 hours
Enter 1ml 3- aminopropyl triethoxysilanes, fully after reaction 12 hours, repeatedly 10 are washed and centrifuged with absolute ethyl alcohol
Time, then vacuum drying obtains the LiNi of surface active0.5Mn1.5O4Powder.
By the LiNi of the surface active of acquisition0.5Mn1.5O4It is anhydrous that powder and 0.070 gram of thioacetamide are scattered in 100ml
In ethyl alcohol, ammonium hydroxide is instilled under stirring later, adjusts the pH value of solution, the PH values of solution are controlled 8.5.Fully reaction 4
After hour, is washed, centrifuged with absolute ethyl alcohol, being then dried to obtain adsorption has the LiNi of sulphion0.5Mn1.5O4Powder
End.
Adsorption is had to the LiNi of sulphion0.5Mn1.5O4Powder is placed in atmosphere furnace, is burnt under argon atmosphere
Knot, sintering temperature are 400 DEG C, and the heating rate that sintering temperature is raised to from room temperature is 3 DEG C/min, and sintering time is 12 hours；
It is cooled to room temperature with stove after sintering, obtains the LiNi of surface sulfide0.5Mn1.5O4Positive electrode.
Fig. 1 is the X-ray diffracting spectrum that the implementation case prepares sample, as shown in Figure 1.By the collection of illustrative plates it is found that being closed
At powder diffraction maximum it is sharp, and the ratio of (111) diffraction peak intensity and (311) diffraction peak intensity is more than 1.5, explanation
LiNi0.5Mn1.5O4The crystallinity of powder sample is very high.Surface in situ be modified composite material XRD spectrum in addition to
LiNi0.5Mn1.5O4Diffraction maximum outside, be also observed with diffraction maximum at 27.62 °, through control be MnS2Most strong main peak.
LiNi prepared by the implementation case0.5Mn1.5O4Powder sample carries out electron-microscope scanning, as shown in Fig. 2 (a).
LiNi0.5Mn1.5O4The stereoscan photograph of powder shows LiNi obtained0.5Mn1.5O4Powder has smooth regular in surface
Polyhedral structure.
LiNi after surface sulfide prepared by the implementation case0.5Mn1.5O4Powder sample carries out electron-microscope scanning, such as Fig. 2
(b) shown in.LiNi after surface sulfide0.5Mn1.5O4The stereoscan photograph of powder is shown, to LiNi0.5Mn1.5O4Carry out surface
There is surface coating in its surface after in-situ modified.
LiNi made from weighing 0.08 gram0.5Mn1.5O4Powder, 0.01 gram of conductive black and 0.01 gram of binder PVDF are (poly-
Vinylidene), it is scattered in N-Methyl pyrrolidone solution, is applied on aluminium foil after mixing, 12 are dried in vacuo in 120 DEG C
Hour, LiNi is made0.5Mn1.5O4Anode.Use the LiPF6/EC/DEC/DMC of 1.0mol/L for electrolyte, wherein LiPF6For
Conductive salt, EC (ethylene carbonate)/DEC (diethyl carbonate)/DMC (dimethyl carbonate) are double solvents, the volume ratio of three
(EC:DEC:DMC it is) 1： 1：1.It is diaphragm by cathode, 2300 polypropylene screens of Cellgard of metal lithium sheet, with above-mentioned anode
It is assembled into button cell, charge and discharge are carried out with 2C (1C=148mA/g) current density, the voltage ranges of charge and discharge is 3.0~
4.9V.The LiNi after surface sulfide is assembled with same steps0.5Mn1.5O4Button cell.
Fig. 3 is charge and discharge cycles figure, as seen from the figure, the LiNi under 25 DEG C, 2C multiplying powers0.5Mn1.5O4The electric discharge specific volume of material
Amount can reach 120mAh/g, illustrate LiNi made from this method0.5Mn1.5O4Material has good chemical property.
LiNi0.5Mn1.5O4Capacity retention ratio is 45.3% after recycling 1800 times, the LiNi after surface sulfide0.5Mn1.5O4Cycle 2500 times
Capacity retention ratio is 74.9% afterwards, illustrates that this method can largely improve LiNi0.5Mn1.5O4Cyclical stability.
Embodiment 2
2.918 grams of nickel nitrates are weighed, 7.364 grams of manganese acetates and 1.421 grams of lithium nitrates are dissolved in 400ml deionized waters
In, it is added after persistently stirring 30 minutes at room temperature and weighs 12.621 grams of citric acids, instilled ethylenediamine in stirring, adjust molten
The pH value of the pH value of liquid, solution is controlled 6.8 or so, is then stirred continuously until to obtain gel liquid under 85 DEG C of water-baths.
Gel liquid is placed in 16 hours dry in the air dry oven that temperature is 260 DEG C, the puffy that will then be obtained after drying
Substance is ground, and obtains Gel Precursor powder.The Gel Precursor powder being collected into is placed in Muffle furnace, in air
It is calcined under atmosphere：First with the heating rate of 3 DEG C/s rise to 550 DEG C from room temperature, after being sintered 5 hours at 550 DEG C again with 3 DEG C/
The heating rate of minute rises to 900 DEG C, is calcined 15 hours at 900 DEG C.It is naturally cooling to room temperature with stove after calcining, is taken out
Powder, grinding and sieving obtain LiNi0.5Mn1.5O4Positive electrode.
Weigh 0.024 gram of LiNi0.5Mn1.5O4Powder is simultaneously scattered in 200ml absolute ethyl alcohols, and ultrasonic vibration adds after 2 hours
Enter 2ml 3- aminopropyl triethoxysilanes, after fully reacting 8 hours, washed and centrifuged with absolute ethyl alcohol 10 times repeatedly,
Then vacuum drying obtains the LiNi of surface active0.5Mn1.5O4Powder.By the LiNi of the surface active of acquisition0.5Mn1.5O4Powder
It is scattered in 100ml absolute ethyl alcohols with 0.141 gram of thioacetamide, instills ammonium hydroxide under stirring later, adjust solution
The pH value of pH value, solution is controlled 8.0.Fully after reaction 3 hours, is washed, centrifuged with absolute ethyl alcohol, it is then dry
There is the LiNi of sulphion to adsorption0.5Mn1.5O4Powder.Adsorption is had to the LiNi of sulphion0.5Mn1.5O4Powder is placed in
It in atmosphere furnace, is sintered under argon hydrogen gaseous mixture atmosphere, sintering temperature is 450 DEG C, and the liter of sintering temperature is raised to from room temperature
Warm rate is 3 DEG C/min, and sintering time is 10 hours；It is cooled to room temperature with stove after sintering, obtains surface sulfide
LiNi0.5Mn1.5O4Positive electrode.
Fig. 4 (a) is LiNi0.5Mn1.5O4The stereoscan photograph of powder shows LiNi obtained0.5Mn1.5O4Powder has
The smooth regular polyhedral structure in surface.Fig. 5 (b) is the LiNi of surface sulfide0.5Mn1.5O4The stereoscan photograph of powder,
Compared to LiNi0.5Mn1.5O4, the sample surfaces of surface sulfide are with the presence of particulate matter.
LiNi made from weighing 0.08 gram0.5Mn1.5O4Powder, 0.01 gram of conductive black and 0.01 gram of binder PVDF are (poly-
Vinylidene), it is scattered in N-Methyl pyrrolidone solution, is applied on aluminium foil after mixing, 12 are dried in vacuo in 120 DEG C
Hour, LiNi is made0.5Mn1.5O4Anode.Use the LiPF6/EC/DEC/DMC of 1.0mol/L for electrolyte, wherein LiPF6For
Conductive salt, EC (ethylene carbonate)/DEC (diethyl carbonate)/DMC (dimethyl carbonate) are double solvents, the volume ratio of three
(EC:DEC:DMC it is) 1： 1：1.It is diaphragm by cathode, 2300 polypropylene screens of Cellgard of metal lithium sheet, with above-mentioned anode
It is assembled into button cell, charge and discharge are carried out with 2C (1C=148mA/g) current density, the voltage ranges of charge and discharge is 3.0~
4.9V.The LiNi after surface sulfide is assembled with same steps0.5Mn1.5O4Button cell.
Fig. 5 is charge and discharge cycles figure, as seen from the figure, the LiNi under 25 DEG C, 2C multiplying powers0.5Mn1.5O4The electric discharge specific volume of material
Amount can reach 125mAh/g, illustrate LiNi made from this method0.5Mn1.5O4Material has good chemical property.
LiNi0.5Mn1.5O4Capacity retention ratio is 69.1% after recycling 500 times, the LiNi after surface sulfide0.5Mn1.5O4After cycle 500 times
Capacity retention ratio is 80%, illustrates that this method can largely improve LiNi0.5Mn1.5O4Cyclical stability.
Claims (7)
1. a kind of method in spinel nickel manganate cathode material for lithium surface sulfide, it is characterised in that：
1）The compound of soluble Li, Ni, Mn are pressed respectively（1~ x）:0.5:1.5 molar ratios are dissolved in deionized water, are sufficiently stirred
Clear mixed solution is obtained, wherein 0≤x≤0.1;
2）Metal ion chelating drug is added in mixed solution and stirs 6~10 hours, ammonium hydroxide or ethylenediamine is used to adjust later
The pH value of solution is stated, pH range is 6~7；
3）Mixed solution is positioned in the water-bath that temperature is 80~90 DEG C and continues to stir and flow back, after stirring 8~24 hours
Obtain gel liquid；
4）Gel liquid is placed in air dry oven or Muffle furnace, 8~24 are heat-treated under 250~280 DEG C of air atmosphere
Puffy substance is obtained after hour, it is ground to obtain Gel Precursor powder；
5）The Gel Precursor powder being collected into is placed in Muffle furnace or atmosphere furnace, under air or oxygen atmosphere in two stages
Calcining, is cooled to room temperature with stove after calcining, obtains nickel lithium manganate cathode material：
6）The nickel lithium manganate cathode material powder of preparation is scattered in absolute ethyl alcohol, 3- is added after 2~6 hours in ultrasonic vibration
Aminopropyl triethoxysilane is washed with absolute ethyl alcohol, is centrifuged, be then dried to obtain table after fully reacting 5~15 hours
The nickel ion doped powder of face activation；
7）The nickel ion doped powder and thioacetamide for weighing the surface active of certain mass are scattered in absolute ethyl alcohol, Zhi Houyong
Ammonium hydroxide or ethylenediamine adjust the pH value of solution, and pH range is 7.5~8.5, after reaction 3 ~ 6 hours, washed with absolute ethyl alcohol, from
The heart detaches, and being then dried to obtain adsorption has the nickel ion doped powder of sulphion；
8）There is the nickel ion doped powder of sulphion to be placed in atmosphere furnace adsorption, under argon gas or argon hydrogen gaseous mixture atmosphere into
Row sintering, sintering temperature are 300 ~ 500 DEG C, and the heating rate that sintering temperature is raised to from room temperature is 1 ~ 5 DEG C/min, sintering time
It is 8 ~ 15 hours；It is cooled to room temperature with stove after sintering, obtains the nickel lithium manganate cathode material of surface sulfide.
2. a kind of method in spinel anode material surface sulfide according to claim 1, it is characterised in that described
Soluble Li compounds are one kind in lithium acetate, lithium nitrate and lithium sulfate.
3. a kind of method in spinel anode material surface sulfide according to claim 1, it is characterised in that described
Soluble Ni compounds are one kind in nickel acetate, nickel nitrate and nickel sulfate.
4. a kind of method in spinel anode material surface sulfide according to claim 1, it is characterised in that described
Soluble M n compounds are one kind in manganese acetate, manganese nitrate and manganese sulfate.
5. a kind of method in spinel anode material surface sulfide according to claim 1, it is characterised in that described
Metal ion chelating drug is the one kind for referring to oxalic acid, citric acid, tartaric acid, and the dosage of metal ion intercalating agent is institute in mixed solution
There are 2.0~4.0 times of metal ion species mole summation.
6. a kind of method in spinel anode material surface sulfide according to claim 1, it is characterised in that described
The dosage of 3- aminopropyl triethoxysilanes is that 0.03 gram of nickel ion doped needs 0.5 ~ 3ml 3- aminopropyl triethoxysilanes.
7. a kind of method in spinel anode material surface sulfide according to claim 1, it is characterised in that described
Two benches are calcined, the first stage：Calcination temperature is 450 ~ 550 DEG C, and the heating rate that calcination temperature is raised to from room temperature is 1~5
DEG C/min, calcination time is 3~8 hours；Second stage：Calcination temperature is 850~950 DEG C, from first stage calcination temperature liter
Heating rate to second stage calcination temperature is 2~5 DEG C/min, and calcination time is 9~20 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810179127.2A CN108400320B (en) | 2018-03-05 | 2018-03-05 | Method for vulcanizing surface of spinel lithium nickel manganese oxide positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810179127.2A CN108400320B (en) | 2018-03-05 | 2018-03-05 | Method for vulcanizing surface of spinel lithium nickel manganese oxide positive electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108400320A true CN108400320A (en) | 2018-08-14 |
| CN108400320B CN108400320B (en) | 2020-07-10 |
Family
ID=63092286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810179127.2A Expired - Fee Related CN108400320B (en) | 2018-03-05 | 2018-03-05 | Method for vulcanizing surface of spinel lithium nickel manganese oxide positive electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108400320B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755551A (en) * | 2019-03-13 | 2019-05-14 | 桑顿新能源科技有限公司 | Surface clad anode material and preparation method thereof and battery |
| CN111193018A (en) * | 2020-01-11 | 2020-05-22 | 松山湖材料实验室 | Lithium battery positive active material and preparation method and application thereof |
| CN113845152A (en) * | 2021-08-30 | 2021-12-28 | 蜂巢能源科技有限公司 | Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery |
| CN114976007A (en) * | 2022-06-08 | 2022-08-30 | 中国科学院化学研究所 | Method for controllably constructing sulfide coating layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7771497B1 (en) * | 2005-01-19 | 2010-08-10 | Greatbatch Ltd. | Method of using cyclic pressure to increase the planarity of SVO/current collector/CFX electrodes for use in lithium electrochemical cells |
| CN104752702A (en) * | 2015-03-16 | 2015-07-01 | 长沙矿冶研究院有限责任公司 | Cathode material of lithium sulphur battery, preparation method of cathode material, cathode of lithium sulphur battery and lithium sulphur battery |
| CN105789568A (en) * | 2014-12-16 | 2016-07-20 | 绍兴文理学院 | Sulfur element doped lithium-rich lithium manganese oxide material and preparation method thereof |
| CN106711455A (en) * | 2016-11-28 | 2017-05-24 | 德阳九鼎智远知识产权运营有限公司 | Sulfurized amino polymer anode material and lithium ion battery prepared from thereof |
-
2018
- 2018-03-05 CN CN201810179127.2A patent/CN108400320B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7771497B1 (en) * | 2005-01-19 | 2010-08-10 | Greatbatch Ltd. | Method of using cyclic pressure to increase the planarity of SVO/current collector/CFX electrodes for use in lithium electrochemical cells |
| CN105789568A (en) * | 2014-12-16 | 2016-07-20 | 绍兴文理学院 | Sulfur element doped lithium-rich lithium manganese oxide material and preparation method thereof |
| CN104752702A (en) * | 2015-03-16 | 2015-07-01 | 长沙矿冶研究院有限责任公司 | Cathode material of lithium sulphur battery, preparation method of cathode material, cathode of lithium sulphur battery and lithium sulphur battery |
| CN106711455A (en) * | 2016-11-28 | 2017-05-24 | 德阳九鼎智远知识产权运营有限公司 | Sulfurized amino polymer anode material and lithium ion battery prepared from thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755551A (en) * | 2019-03-13 | 2019-05-14 | 桑顿新能源科技有限公司 | Surface clad anode material and preparation method thereof and battery |
| CN109755551B (en) * | 2019-03-13 | 2023-05-09 | 湖南桑瑞新材料有限公司 | Surface-coated positive electrode material, preparation method thereof and battery |
| CN111193018A (en) * | 2020-01-11 | 2020-05-22 | 松山湖材料实验室 | Lithium battery positive active material and preparation method and application thereof |
| CN111193018B (en) * | 2020-01-11 | 2021-08-17 | 松山湖材料实验室 | Lithium battery positive active material and preparation method and application thereof |
| CN113845152A (en) * | 2021-08-30 | 2021-12-28 | 蜂巢能源科技有限公司 | Lithium nickel manganese oxide positive electrode material, preparation method thereof and lithium ion battery |
| CN114976007A (en) * | 2022-06-08 | 2022-08-30 | 中国科学院化学研究所 | Method for controllably constructing sulfide coating layer |
| CN114976007B (en) * | 2022-06-08 | 2024-02-20 | 中国科学院化学研究所 | Method for controllably constructing sulfide coating layer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108400320B (en) | 2020-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109742377B (en) | Method for surface modification of high-nickel ternary positive electrode material | |
| CN105990577B (en) | A kind of anode material for lithium-ion batteries LiNi0.6-xCo0.2Mn0.2AlxO2-yFyAnd preparation method thereof | |
| CN106684323A (en) | Ternary lithium-ion battery cathode material improved by active oxide multiply and preparation method thereof | |
| CN108448109B (en) | Layered lithium-rich manganese-based positive electrode material and preparation method thereof | |
| CN105140492A (en) | Cobalt-nickel lithium manganate composite positive electrode material with surface wrapped by lithium zirconate and preparation method | |
| CN105024067B (en) | Lithium ion battery, composite doped modified positive active material thereof and preparation method | |
| CN104466102B (en) | A kind of porous V2O5/C complex microspheres of positive electrode material of lithium secondary cell and preparation method thereof | |
| CN106654223A (en) | Modification method for tungsten-containing compound coated positive electrode material of lithium ion battery | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN108400320A (en) | A method of in spinel nickel manganate cathode material for lithium surface sulfide | |
| CN103390748B (en) | A kind of preparation method of alumina-coated lithium cobaltate cathode material | |
| CN105576231A (en) | High-voltage lithium oil battery positive electrode material with spinel structure and preparation method of high-voltage lithium oil battery positive electrode material | |
| CN104979549A (en) | Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material | |
| CN107204426A (en) | A kind of cobalt nickel oxide manganses lithium/titanate composite anode material for lithium of zirconium doping vario-property | |
| CN103825014B (en) | A kind of preparation method of high-voltage anode material of lithium ion batteries lithium nickel manganese composite oxide | |
| CN105304894A (en) | Method for preparing high-performance lithium manganite positive electrode material by compound doping | |
| CN108039486A (en) | The hollow core shell structure vanadic anhydride anode electrode piece of tremelliform and its fastening lithium ionic cell preparation method | |
| CN104577090A (en) | Method for preparing carbon and oxide composite modified lithium titanate material | |
| CN107768628B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN111799465B (en) | Composite coating method for manganese-based lithium battery electrode material | |
| CN110563052B (en) | Preparation method of carbon and lanthanum oxide co-coated modified lithium nickel manganese oxide positive electrode material | |
| CN114203993B (en) | Li (lithium ion battery) 2 SeO 4 Fast ion conductor modified lithium ion battery anode material | |
| CN107834054B (en) | Preparation method of lithium nickel manganese oxide-graphene composite material for lithium ion battery | |
| CN105185969B (en) | A kind of positive electrode and preparation method thereof | |
| CN108682800A (en) | A kind of nickelic ternary modified anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200710 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |