CN106784740A - A kind of hollow ball positive electrode and preparation method thereof - Google Patents
A kind of hollow ball positive electrode and preparation method thereof Download PDFInfo
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- CN106784740A CN106784740A CN201710084879.6A CN201710084879A CN106784740A CN 106784740 A CN106784740 A CN 106784740A CN 201710084879 A CN201710084879 A CN 201710084879A CN 106784740 A CN106784740 A CN 106784740A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- 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
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- H—ELECTRICITY
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- 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
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Abstract
The present invention relates to the synthesis of anode material for lithium-ion batteries, a kind of hollow ball positive electrode and preparation method thereof is proposed.The first mixed liquor containing glucose and nickel sulfate ammonia is obtained into the first suspension through hydro-thermal reaction；First suspension is obtained the first precipitation of medicine ball through dried process；First precipitation calcining is obtained the nickel protoxide forerunner of hollow ball；Manganese acetate, lithium acetate and solvent are mixed, the second mixed liquor is obtained；And the blended evaporation of the second mixed liquor and nickel protoxide forerunner is obtained into the second precipitation, and the second precipitation calcine and obtains hollow ball positive electrode, above-mentioned positive electrode is piled up by nano level primary particle and forms micron-sized hollow ball second particle.The micron order matrix structure of hollow ball-shape can slow down primary particle dissolving in the electrolytic solution in ceaselessly cyclic process so that hollow ball positive electrode is less likely to occur to collapse in cyclic process, shows excellent chemical property.
Description
Technical field
The present invention relates to field of lithium ion battery anode, in particular to a kind of hollow ball positive electrode and its
Preparation method.
Background technology
Lithium ion battery is a kind of rechargeable battery, and relatively broad application has been obtained at present.Lithium ion battery one
As by positive pole, negative pole, barrier film, electrolyte and battery container etc. part constitute, the cost of wherein positive electrode accounts for battery 40%
More than, but the specific capacity of positive electrode is but well below the specific capacity of negative material, thus lithium battery has weight under study for action
The application value wanted.
Due to transition metal oxide LiMO2(compositions of several elements of M=Co, Mn, Ni) are in cycle performance, cost and system
The aspects such as standby technique are not ideal enough, especially lower-cost LiMnO in three2The phase transformation produced in cyclic process causes electricity
Pressure and discharge capacity decay.Consideration based on structural stability and cost, some researchers trial prepares cheap
Li2MnO3And LiMO2Solid-solution material, the ratio of such material Mn is big, and material cost is relatively low and rich in lithium, therefore is referred to as richness
Lithium material.
(typical chemical formula is xLi to lithium-rich manganese-based anode material2MnO3-(1-x)LiMO2, wherein M=Ni, Co, Mn etc. are several
The combination of transition metal), it is α-NaFeO2The side's layer structure of type six (space group R-3m (166)), its discharge capacity is up to
250mAh g-1, thus received much concern in battery research system in recent years.Studied in lithium-rich manganese-based anode material more
Materials chemistry formula be 0.5Li2MnO3-0.5LiNi0.5Mn0.5O2, reason is that it has specific discharge capacity higher, and compositionization
There is no cobalt element in element, thus it is safe and nontoxic.But lithium-rich manganese-based anode material there is also following shortcoming：1. cyclicity
Energy, high rate performance are poor；2. irreversible capacity is big first；3. voltage attenuation is serious.These problems are all serious to constrain above-mentioned material
The industrial applications of material.
The content of the invention
It is an object of the invention to provide a kind of hollow ball positive electrode, it is piled up by nano level primary particle and forms tool
There is the micron order hollow ball of nano-micro structure.The micron order matrix structure of hollow ball-shape can slow down and not stop in cyclic process once
Grain dissolving in the electrolytic solution so that hollow ball positive electrode is less likely to occur to collapse in cyclic process, shows good
Structural stability and excellent cycle performance and high rate performance.
Another object of the present invention is to provide a kind of preparation method of above-mentioned hollow ball positive electrode, using above-mentioned preparation
Hollow ball positive electrode obtained in method has nano-micro structure, and shows excellent cycle performance and high rate performance.
What embodiments of the invention were realized in：
A kind of preparation method of hollow ball positive electrode, it is comprised the following steps：
The first mixed liquor containing glucose and nickel sulfate ammonia is obtained into the first suspension through hydro-thermal reaction；First is suspended
Liquid obtains the first precipitation of medicine ball through dried process；First precipitation calcining is obtained the nickel protoxide forerunner of hollow ball；
Manganese acetate, lithium acetate and solvent are mixed, the second mixed liquor is obtained；And
The blended evaporation of second mixed liquor and nickel protoxide forerunner is obtained into the second precipitation, the second precipitation is calcined.
Preferably, 20~24h is incubated after hydro-thermal reaction is warming up to 180 DEG C~200 DEG C with the heating rate of 3~4 DEG C/min,
And room temperature is down to the rate of temperature fall of 3~5 DEG C/min.
Preferably, hydro-thermal reaction is carried out under agitation, and mixing speed is 400~500r/min.
Preferably, the mol ratio of glucose and nickel sulfate ammonia is 220~230mol：45~46mol.
Preferably, the second mixed liquor and the amount ratio of nickel protoxide forerunner are 180~200ml：6.20~6.23g, wherein
The amount ratio of manganese acetate, lithium acetate and solvent is 0.25mol in second mixed liquor：0.60~0.65mol：6.20~6.23g.
Preferably, the number of times of mixing evaporation is multiple, the number of times of the second mixed liquor correspondence mixing evaporation is divided into many parts, often
Secondary mixing evaporation includes：To added in the evaporation equipment containing nickel protoxide forerunner any a second mixed liquor be well mixed,
After sealed insulation, intensification is evaporated.
Preferably, the second mixed liquor is carried out with the mixed process of nickel protoxide forerunner under ultrasound, stirring and heat-retaining condition.
Preferably, ultrasonic intensity is 40~50KHz, and the rotating speed of stirring is 450~500r/min, and the condition of insulation is 60
5~6h of constant temperature at~65 DEG C.
Preferably, the volume ratio of water-ethanol mixed solvent reclaimed water and ethanol is 9:1~8:2.
A kind of hollow ball positive electrode, is obtained using the preparation method of above-mentioned hollow ball positive electrode.
The beneficial effect of the hollow ball positive electrode of the embodiment of the present invention and preparation method thereof is：Obtain micro- by hydro-thermal method
First precipitation of rice ball, micron ball calcining is obtained the nickel protoxide forerunner of hollow ball.Then by stirring manganese acetate and second
Sour lithium is wrapped on material granule.The migration of ion and the decomposition of acetate are realized eventually through high-temperature calcination, has synthesized hollow
Ball positive electrode.In addition the invention further relates to a kind of hollow ball positive electrode, wherein hollow ball positive electrode has nano-micro structure,
Above-mentioned positive electrode is piled up by nano level primary particle and forms micron-sized hollow ball second particle.Formed between primary particle
Loose structure can strengthen electrolyte to the infiltration in nano particle, while the micron order matrix structure of hollow ball-shape can subtract
Primary particle dissolving in the electrolytic solution in slow ceaselessly cyclic process so that hollow ball positive electrode is not allowed in cyclic process
Easily collapse, show good structural stability, thus material capacity attenuation in continuous charge and discharge process is smaller, table
Reveal excellent cycle performance and high rate performance.
Brief description of the drawings
Technical scheme in order to illustrate more clearly the embodiments of the present invention, below will be attached to what is used needed for embodiment
Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, thus be not construed as it is right
The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this
A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the XRD of the hollow ball positive electrode that the embodiment of the present invention 1 is provided；
Fig. 2 is the SEM figures of the first precipitation that the embodiment of the present invention 1 is provided；
Fig. 3 is the SEM figures of the hollow ball positive electrode that the embodiment of the present invention 1 is provided；
Fig. 4 is first charge and discharge of the hollow ball positive electrode of the offer of the embodiment of the present invention 1 under 2.0~4.8V voltage ranges
Electric curve；
Fig. 5 is high rate performance of the hollow ball positive electrode of the offer of the embodiment of the present invention 1 under 2.0~4.8V voltage ranges
Figure；
Fig. 6 is hollow ball positive electrode 0.5C circulations 50 under 2.0~4.8V voltage ranges that the embodiment of the present invention 1 is provided
Secondary cycle performance figure.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products that can be obtained by commercially available purchase.
Hollow ball positive electrode of the embodiment of the present invention and preparation method thereof is specifically described below.
The invention provides a kind of preparation method of hollow ball positive electrode, it includes preparing nickel protoxide forerunner, prepares
Second mixed liquor and prepare hollow ball positive electrode.
S1, prepare nickel protoxide forerunner：
The first mixed liquor containing glucose and nickel sulfate ammonia is obtained into the first suspension through hydro-thermal reaction；First is suspended
Liquid obtains the first precipitation of medicine ball through dried process；First precipitation calcining is obtained the nickel protoxide forerunner of hollow ball；
Specifically, preparation, the preparation of first suspension, first of the nickel protoxide precursor step including the first mixed liquor are prepared
The preparation of precipitation and the preparation of nickel protoxide forerunner.
The preparation of S101, the first mixed liquor：
Take glucose and the dissolving of nickel sulfate ammonia obtains the first mixed solution in deionized water, by the first mixed solution in magnetic
Stirred under power stirring；
Wherein, the mol ratio of glucose and nickel sulfate ammonia is 220~230mol：45~46mol.
The preparation of S102, the first suspension：
The first suspension is obtained by hydro-thermal reaction is carried out in above-mentioned first mixed solution immigration water heating kettle；
Wherein, after being warming up to 180 DEG C~200 DEG C with the heating rate of 3~4 DEG C/min in hydrothermal reaction process insulation 20~
24h, and room temperature is down to the rate of temperature fall of 3~5 DEG C/min.And above-mentioned hydro-thermal reaction is carried out under agitation.Mixing speed
It is 400~500r/min, it is preferable that mixing speed is 450r/min.Under so moderate mixing speed, the original in water heating kettle
Material can sufficiently be mixed, and the atom in mixed liquor can quickly reach homogeneous in the state of stirring.Avoid solution
In ion rely on ion diffusion motion, cause solution concentration heterogeneity.Soaking time and temperature, and rate of temperature fall is to hydro-thermal
It is critical that parameter for reaction.In hydro-thermal reaction, the ion in solution is tied again in the environment of HTHP
It is brilliant.The size of soaking time and temperature directly affects the size and pattern and crystallinity of grain crystalline, and then influences material
Chemical property.Hydrothermal temperature in the present invention is 180~200 DEG C, and the time is 20~24h so that the particle for obtaining is
The good nano particle of crystallinity.The speed often lowered the temperature in water-heat process has lost focus, but actually hydro-thermal reaction
Rate of temperature fall all has a certain impact to the surface crystallinity and granularity of material.Appropriate rate of temperature fall can cause crystal in temperature
Further growth or precipitation with the environment of, are also the means for controlling crystal habit.
The preparation of S103, the first precipitation：
The precipitation obtained after first suspension is filtered is washed with water 3 times respectively, and ethanol is washed 2 times.Wherein, water can be
Deionized water, pure water or distilled water, it is preferable that water is deionized water.Being deposited in 100 DEG C in vacuum drying chamber after by washing
Dry 10h and obtain the first precipitation.Deionized water washing can remove the foreign ion in water, and ethanol washing can take away deionization
The moisture remained in washing process, makes follow-up drying process faster more thorough.
S104, the preparation of nickel protoxide forerunner：
First precipitation is put into corundum magnetic boat and is calcined under air atmosphere in tube furnace, tube furnace is with the liter of 5 DEG C/min
Warm speed is incubated 2~3h and obtains nickel protoxide forerunner after being warming up to 500~550 DEG C.
S2, the second mixed liquor of preparation：
Manganese acetate, lithium acetate and solvent are mixed, the second mixed liquor is obtained.
Specifically, manganese acetate and lithium acetate dissolving obtained into the second mixed liquor in a solvent, wherein solvent can be from
The volume ratio of the mixed solvent of sub- water, or water-ethanol, water and ethanol is 9:1~8:2；Manganese acetate in second mixed liquor,
The amount ratio of lithium acetate and solvent is 0.25mol：0.60~0.65mol：6.20~6.23g.
S3, prepare hollow ball positive electrode：
The blended evaporation of second mixed liquor and nickel protoxide forerunner is obtained into the second precipitation, the second precipitation is calcined.
Specifically, preparing hollow ball positive electrode step includes placing nickel protoxide forerunner, mixing evaporation, calcination process.
S301, placement nickel protoxide forerunner：
Nickel protoxide forerunner is placed in evaporation equipment, evaporation equipment can be flat bottom beaker, round bottom beaker, round bottom burning
Bottle, preferably round bottom beaker, round bottom beaker dead angle small volume in whipping process, are conducive to nickel protoxide forerunner with solution
Uniform mixing.
S302, mixing evaporation：
Second mixed liquor is mixed with nickel protoxide forerunner under ultrasound, stirring and heat-retaining condition, then heat up ultrasonic bar
Part lower open mouth is stirred to being evaporated completely；
Wherein, the second mixed liquor and the amount ratio of nickel protoxide forerunner are 180~200ml：6.20~6.23g.It is above-mentioned super
The ultrasound intensity of sound is 40~50KHz, and the rotating speed of stirring is 450~500r/min, when holding temperature at 60~65 DEG C to be incubated
Between be 5~6h, heat up evaporation when heating rate be 80~87 DEG C/min.
Above-mentioned mixing evaporation can be one or many, in the present embodiment, before the mixed liquor of preferred pair second and nickel protoxide
Drive carries out repeatedly mixing evaporation.Specifically, the number of times by the correspondence mixing evaporation of the second mixed liquor is divided into many parts.To sub- containing oxidation
Add any a second mixed liquor to be well mixed in the evaporation equipment of nickel forerunner, be incubated under sealing, stirring condition, then
Intensification is evaporated, and then takes in a second mixed liquor addition evaporation equipment in addition, is incubated under sealing, stirring condition, then
Intensification is evaporated.Repeat the above steps, add a second mixed liquor after being evaporated every time in evaporation equipment, until all of second
Mixed liquor is used up, and the second precipitation is obtained.
Mixing evaporation is illustrated below：
Wherein, the number of the second mixed liquor is 3 parts or 4 parts, and the second mixed liquor can be distributed in equal volume, it is also possible to by one
Fixed volume ratio distribution, more preferred is by volume 1:2:4 divide, and the second mixed liquor is added in round bottom beaker by several times, can
To cause that manganese acetate and lithium acetate in the second mixed liquor are slowly separated out on the surface of nickel protoxide forerunner, so multiple precipitation
Can cause that lithium acetate and manganese acetate are uniformly deposited in the particle surface of nickel protoxide forerunner.Preferably, with 1:2:4 volume
Than the second mixed liquor is separated, number volume is added gradually to increase.Grain diameter gradually increases, and increases the body of the second mixed liquor
Product, is conducive to lithium acetate and manganese acetate more preferably to precipitate faster, meets the requirement of particle growth.
S303, calcination process
Second precipitation obtains hollow ball positive electrode 0.5Li through 500 DEG C of calcinings 5h, 750 DEG C of 5h after 900 DEG C of 10h2MnO3-
0.5LiNi0.5Mn0.5O2。
The invention provides a kind of hollow ball positive electrode, it is obtained using the preparation method of above-mentioned hollow ball positive electrode,
It has nano-micro structure, and above-mentioned positive electrode is piled up by nano level primary particle and forms micron-sized hollow ball second particle.
The loose structure formed between primary particle can strengthen electrolyte to the infiltration in nano particle, while the micron of hollow ball-shape
Level matrix structure can slow down primary particle dissolving in the electrolytic solution in ceaselessly cyclic process so that hollow ball positive electrode
It is less likely to occur to collapse in cyclic process, shows good structural stability, and excellent chemical property.
For lithium-rich manganese-based anode material, (typical chemical formula is xLi to the hollow ball positive electrode that the present invention is provided2MnO3-(1-
x)LiMO2, the combination of several transition metals such as wherein M=Ni, Co, Mn), it is α-NaFeO2The side's layer structure of type six is (empty
Between group R-3m (166)), specific discharge capacity is up to 250mAh g-1, thus received much concern in anode material of lithium battery field.Wherein
0.5Li2MnO3-0.5LiNi0.5Mn0.5O2Cause does not have cobalt element in having specific discharge capacity higher, and constitutional chemistry element, because
And it is safe and nontoxic, obtain the favor of researcher.
Feature of the invention and performance are described in further detail with reference to embodiments.
Embodiment 1
The present embodiment provides a kind of preparation method of hollow ball positive electrode, comprises the following steps：
S1, prepare nickel protoxide forerunner：
Take 228mmol glucose and 45.6mmol nickel sulfate ammonia is dissolved in 360ml deionized waters that to obtain the first mixing molten
Liquid, the first mixed solution is stirred under magnetic stirring；By above-mentioned first mixed liquor move into 500ml water heating kettles in,
Under the mixing speed of 500r/min, 180 DEG C are warming up to the heating rate of 4 DEG C/min, 180 DEG C of reaction 24h are incubated, then with 3
DEG C/rate of temperature fall of min is cooled to room temperature, obtains the first suspension；First suspension is precipitated through filtering, precipitation is used
Deionized water is washed 3 times, and ethanol is washed 2 times, and obtains the first precipitation after being vacuum dried 10h at 100 DEG C in the vacuum drying chamber；
Above-mentioned first precipitation is put into corundum magnetic boat in tube furnace pyrolytic under air atmosphere, tube furnace is controlled with 5 DEG C/min's
Heating rate is incubated 2h and obtains nickel protoxide forerunner after being warming up to 500 DEG C；
S2, the second mixed liquor of preparation：
Weigh 0.25mol manganese acetates and 0.6mol lithium acetates, and be dissolved in obtaining second in 200ml deionized waters mixing
Close liquid；
S3, prepare hollow ball positive electrode：
Second mixed liquor is equally divided into 3 parts, 6.22g nickel protoxides forerunner is weighed and is put into round bottom beaker；To above-mentioned
Add above-mentioned a second mixed liquor in round bottom beaker, rotating speed is 500r/min, under the conditions of ultrasound intensity is 40KHz, first seal
Under the conditions of 60 DEG C of constant temperature 5h, then be warming up to 80 DEG C of open stirrings to being evaporated completely；Repeat to added in round bottom beaker another the
Two mixed liquors are all evaporated to 3 part of second mixed liquor and obtain the second precipitation；By 500 DEG C of high-temperature calcination 5h of the above-mentioned second precipitation, 750
DEG C 5h, 900 DEG C of 10h obtain hollow ball positive electrode 0.5Li2MnO3-0.5LiNi0.5Mn0.5O2。
A kind of hollow ball positive electrode, is obtained using the above method.Using X ' the pert TRO MPD types of Philips Corporate
Polycrystalline turns target x-ray diffractometer (Cu target K alpha rays λ=0.15406nm), and Ni filter plates, tube current is 20mA, and tube voltage is
20kV, θ=10~80 ° of scanning angle 2,8 ° of min of sweep speed-1Hollow ball positive electrode to the present embodiment carries out X-ray
Diffraction, obtains XRD spectrum as shown in Figure 1.Using the S-4800 type SEM of HIT to the present embodiment
First precipitation and hollow ball positive electrode be scanned electronic microscope photos, result such as Fig. 2 and Tu of the ESEM (SEM) for obtaining
Shown in 3, Fig. 2 is the scanning electron microscope (SEM) photograph of the first precipitation, and Fig. 3 is the scanning electron microscope (SEM) photograph of hollow ball positive electrode.Using CR2032 types
Button cell is characterized to the chemical property of synthetic material.First, by active material, conductive agent acetylene black, binding agent
(PVDF mass fractions 10%) is by 80:13:7 mass ratio mixing, is subsequently adding appropriate 1-METHYLPYRROLIDONE for solvent, fills
Divide and stir.The slurry of gained is coated in after lower 120 DEG C of vacuum condition on aluminium foil dries 10h and goes out a diameter of 14mm with sheet-punching machine
Disk, under the conditions of 20Mpa be compacted, obtain button cell positive plate.It is negative with lithium metal in the glove box full of argon gas
Pole, the LiPF of 1mol/L6(volume ratio is 1 to be dissolved in EC-DMC:1) as electrolyte in mixed solution, Celgard2400 is micro-
Hole polypropylene screen is barrier film, and the order assembled according to button cell is obtained button cell.The present embodiment is public using Shenzhen Neware
2.0~4.8V carries out constant current charge-discharge test, wherein 1C=200mAh g to the BTS test systems of department at room temperature-1.Fig. 4 is button
The first charge-discharge curve map of formula battery 0.1C, Fig. 5 is the high rate performance figure of button cell, and Fig. 6 is circulated for material under 0.5C
The cycle performance figure of 50 times.
As can be seen from Figure 1 the main diffraction peak of the hollow ball positive electrode of the present embodiment 1 can index for α-
NaFeO2The side's layer structure of type six (space group R-3m (166)), but having some to index between 21 ° to 25 ° is
Li2MnO3The superlattices weak peak of (space group C2/m), these weak peaks are by Li+And Mn4+Ion is arranged in the superlattices of transition metal layer
Cause, the material for showing synthesis is typical richness lithium material.And the division of the peak of XRD diffraction maximums 006 and 012 is obvious, shows synthesis
Material has good layer structure.
The first of the present embodiment 1 is precipitated as micron ball as can be seen from Figure 2, and its sphericity is good, and size is homogeneous.
The hollow ball positive electrode of the present embodiment 1 is piled into micron ball by nano level primary particle as can be seen from Figure 3,
Its sphericity is good, and size is homogeneous.Can significantly see from the ball of broken shell, the microballoon of synthesis is hollow.
Fig. 4 can be seen that the initial charge curve of the hollow ball positive electrode of the present embodiment has a typical case in 4.4V or so
Platform, the material for showing synthesis is typical lithium-rich anode material, and first discharge specific capacity is 267.8mAh g under its 0.1C-1。
Above-mentioned material is 269.2mAh g in the averaged discharge specific capacity of 0.1C as can be known from Fig. 5 and Fig. 6-1, averagely putting during 10C
Electric specific capacity is 108.1mAh g-1, capability retention 97.4%, first discharge specific capacity is 205.3mAh g during 0.5C-1, follow
Specific discharge capacity is 172.3mAh g after ring time-1, capability retention 83.9%.
Embodiment 2
The present embodiment provides a kind of hollow ball positive electrode, and it is micron-sized hollow that it has nano level primary particle to be piled into
Spherical structure.
The present embodiment provides a kind of preparation method of hollow ball positive electrode, comprises the following steps：
S1, prepare nickel protoxide forerunner：
Take 220mmol glucose and 46mmol nickel sulfate ammonia to be dissolved in 360ml deionizations be that to obtain the first mixing in water molten
Liquid, the first mixed solution is stirred under magnetic stirring；By above-mentioned first mixed liquor move into 500ml water heating kettles in,
Under the mixing speed of 400r/min, 190 DEG C are warming up to the heating rate of 3 DEG C/min, 190 DEG C of reaction 20h are incubated, then with 5
DEG C/rate of temperature fall of min is cooled to room temperature, obtains the first suspension；First suspension is precipitated through filtering, precipitation is used
Deionized water is washed 3 times, and ethanol is washed 2 times, and obtains the first precipitation after being vacuum dried 10h at 100 DEG C in the vacuum drying chamber；
Above-mentioned first precipitation is put into corundum magnetic boat in tube furnace pyrolytic under air atmosphere, tube furnace is controlled with 5 DEG C/min's
Heating rate is incubated 3h and obtains nickel protoxide forerunner after being warming up to 550 DEG C；
S2, the second mixed liquor of preparation：
0.25mol manganese acetates and 0.65mol lithium acetates are weighed, and is dissolved in obtaining second in 190ml deionized waters
Mixed liquor；
S3, prepare hollow ball positive electrode：
Second mixed liquor is equally divided into 3 parts, 6.20g nickel protoxides forerunner is weighed and is put into round bottom beaker；To above-mentioned
Above-mentioned a second mixed liquor is added in round bottom beaker, rotating speed is 450r/min, and ultrasound intensity is under conditions of 50KHz, elder generation is close
65 DEG C of constant temperature 6h under the conditions of envelope, then 85 DEG C of open stirrings are warming up to being evaporated completely；Repeat to adding another in round bottom beaker
Second mixed liquor is all evaporated to 3 part of second mixed liquor and obtains the second precipitation；500 DEG C of high-temperature calcination 5h are precipitated by above-mentioned second,
750 DEG C of 5h, 900 DEG C of 10h obtain hollow ball positive electrode 0.5Li2MnO3-0.5LiNi0.5Mn0.5O2。
Embodiment 3
The present embodiment provides a kind of hollow ball positive electrode, and it is micron-sized hollow that it has nano level primary particle to be piled into
Spherical structure.
The present embodiment provides a kind of preparation method of hollow ball positive electrode, comprises the following steps：
S1, prepare nickel protoxide forerunner：
Take 230mmol glucose and 45mmol nickel sulfate ammonia to be dissolved in 360ml deionizations be that to obtain the first mixing in water molten
Liquid, the first mixed solution is stirred under magnetic stirring；By above-mentioned first mixed liquor move into 500ml water heating kettles in,
Under the mixing speed of 450r/min, 200 DEG C are warming up to the heating rate of 4 DEG C/min, 200 DEG C of reaction 20h are incubated, then with 4
DEG C/rate of temperature fall of min is cooled to room temperature, obtains the first suspension；First suspension is precipitated through filtering, precipitation is used
Deionized water is washed 3 times, and ethanol is washed 2 times, and obtains the first precipitation after being vacuum dried 10h at 100 DEG C in the vacuum drying chamber；
Above-mentioned first precipitation is put into corundum magnetic boat in tube furnace pyrolytic under air atmosphere, tube furnace is controlled with 5 DEG C/min's
Heating rate is incubated 2h and obtains nickel protoxide forerunner after being warming up to 550 DEG C；
S2, the second mixed liquor of preparation：
0.25mol manganese acetates and 0.60mol lithium acetates are weighed, and is dissolved in obtaining second in 180ml deionized waters
Mixed liquor；
S3, prepare hollow ball positive electrode：
Second mixed liquor is equally divided into 4 parts, 6.30g nickel protoxides forerunner is weighed and is put into round bottom beaker；To above-mentioned
Above-mentioned a second mixed liquor is added in round bottom beaker, rotating speed is 470r/min, and ultrasound intensity is under conditions of 45KHz, elder generation is close
60 DEG C of constant temperature 5.5h under the conditions of envelope, then be warming up to 87 DEG C of ultrasound condition lower open mouths and stir to being evaporated completely；Repeat to round bottom beaker
Middle another second mixed liquor of addition is all evaporated to 3 part of second mixed liquor and obtains the second precipitation；500 DEG C are precipitated by above-mentioned second
High-temperature calcination 5h, 750 DEG C of 5h, 900 DEG C of 10h obtain hollow ball positive electrode 0.5Li2MnO3-0.5LiNi0.5Mn0.5O2。
Embodiment 4
The present embodiment provides a kind of hollow ball positive electrode, and it is micron-sized hollow that it has nano level primary particle to be piled into
Spherical structure.
The present embodiment provides a kind of preparation method of hollow ball positive electrode, and it is molten with differring primarily in that for embodiment 3
Solution manganese acetate is different with the solvent of lithium acetate, in S1 steps in the present embodiment, weighs 0.25mol manganese acetates and 0.5mol second
Sour lithium, and be dissolved in obtaining the second mixed liquor in 180ml water-ethanol mixed solvents, the volume ratio of its reclaimed water and ethanol is
9：1.
Embodiment 5
The present embodiment provides a kind of hollow ball positive electrode, and it is micron-sized hollow that it has nano level primary particle to be piled into
Spherical structure.
The present embodiment provides a kind of preparation method of hollow ball positive electrode, and it is molten with differring primarily in that for embodiment 3
Solution manganese acetate is different with the solvent of lithium acetate, in S2 steps in the present embodiment, weighs 0.25mol manganese acetates and 0.60mol
Lithium acetate, and be dissolved in obtaining the second mixed liquor in 180ml water-ethanol mixed solvents, the volume ratio of its reclaimed water and ethanol
It is 8:2.
Embodiment 6
The present embodiment provides a kind of hollow ball positive electrode, and it is micron-sized hollow that it has nano level primary particle to be piled into
Spherical structure.
The present embodiment provides a kind of preparation method of hollow ball positive electrode, and it differs primarily in that S2 with embodiment 3
In step, the second mixed liquor is not separated, during the second mixed liquor disposably added into round bottom beaker.
Embodiment 7
The present embodiment provides a kind of hollow ball positive electrode, and it is micron-sized hollow that it has nano level primary particle to be piled into
Spherical structure.
The present embodiment provides a kind of preparation method of hollow ball positive electrode, and it differs primarily in that S3 with embodiment 3
In step, the second mixed liquor is by volume 1:2:4 points is three parts.
Embodiment 8
The present embodiment provides a kind of hollow ball positive electrode, and it is micron-sized hollow that it has nano level primary particle to be piled into
Spherical structure.
The present embodiment provides a kind of preparation method of hollow ball positive electrode, and it differs primarily in that S3 with embodiment 3
In step, rotating speed is 470r/min, does not carry out ultrasound.
To sum up, the present invention relates to a kind of preparation method of hollow ball positive electrode, the of micron ball is obtained by hydro-thermal method
One precipitation, micron ball calcining is obtained the nickel protoxide forerunner of hollow ball.Then manganese acetate and lithium acetate are wrapped up by stirring
On material granule.The migration of ion and the decomposition of acetate are realized eventually through high-temperature calcination, has synthesized hollow ball positive pole material
Material.In addition the invention further relates to a kind of hollow ball positive electrode, wherein hollow ball positive electrode has nano-micro structure, above-mentioned positive pole
Material is piled up by nano level primary particle and forms micron-sized hollow ball second particle.The porous knot formed between primary particle
Structure can strengthen electrolyte to the infiltration in nano particle, while the micron order matrix structure of hollow ball-shape can slow down ceaselessly
Primary particle dissolving in the electrolytic solution in cyclic process so that hollow ball positive electrode is less likely to occur to collapse in cyclic process
Fall into, show good structure surely, thus material capacity attenuation in continuous charge and discharge process is smaller, shows excellent following
Ring performance and high rate performance.
The preferred embodiments of the present invention are these are only, is not intended to limit the invention, for those skilled in the art
For member, the present invention can have various modifications and variations.All any modifications within the spirit and principles in the present invention, made,
Equivalent, improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of hollow ball positive electrode, it is characterised in that it includes：
The first mixed liquor containing glucose and nickel sulfate ammonia is obtained into the first suspension through hydro-thermal reaction；Described first is suspended
Liquid obtains the first precipitation of medicine ball through dried process；Described first precipitation calcining is obtained the nickel protoxide forerunner of hollow ball；
Manganese acetate, lithium acetate and solvent are mixed, the second mixed liquor is obtained, wherein, the solvent includes aqueous solvent or water-ethanol
Mixed solvent；And
By second mixed liquor it is blended with the nickel protoxide forerunner evaporation obtain the second precipitation, precipitated to described second into
Row calcining.
2. the preparation method of hollow ball positive electrode according to claim 1, it is characterised in that the hydro-thermal reaction is with 3
The heating rate of~4 DEG C/min is incubated 20~24h after being warming up to 180 DEG C~200 DEG C, and is dropped with the rate of temperature fall of 3~5 DEG C/min
To room temperature.
3. the preparation method of hollow ball positive electrode according to claim 2, it is characterised in that the hydro-thermal reaction is being stirred
Carried out under the conditions of mixing, mixing speed is 400~500r/min.
4. the preparation method of the hollow ball positive electrode according to claim any one of 1-3, it is characterised in that the grape
The mol ratio of sugared and described nickel sulfate ammonia is 220~230mol：45~46mol.
5. the preparation method of hollow ball positive electrode according to claim 1, it is characterised in that second mixed liquor with
The amount ratio of the nickel protoxide forerunner is 180~200ml：6.20~6.23g, wherein, second described in second mixed liquor
The amount ratio of sour manganese, the lithium acetate and the solvent is 0.25mol：0.60~0.65mol：6.20~6.23g.
6. the preparation method of hollow ball positive electrode according to claim 1, it is characterised in that the mixing evaporation time
Number is multiple, and the number of times of second mixed liquor correspondence mixing evaporation is divided into many parts, and the mixing evaporation every time includes：
To added in the evaporation equipment containing the nickel protoxide forerunner any portion second mixed liquor be well mixed, sealed guarantor
Wen Hou, intensification is evaporated.
7. the preparation method of hollow ball positive electrode according to claim 6, it is characterised in that second mixed liquor with
The mixed process of the nickel protoxide forerunner is carried out under ultrasound, stirring and heat-retaining condition.
8. the preparation method of hollow ball positive electrode according to claim 7, it is characterised in that the intensity of the ultrasound is
40~50KHz, the rotating speed of the stirring is 450~500r/min, and the condition of the insulation is 5~6h of constant temperature at 60~65 DEG C.
9. the preparation method of hollow ball positive electrode according to claim 1, it is characterised in that the water-ethanol mixing
The volume ratio of solvent reclaimed water and ethanol is 9:1~8:2.
10. a kind of hollow ball positive electrode, it is characterised in that using the hollow ball positive pole material described in claim any one of 1-9
The preparation method of material is obtained.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108511701A (en) * | 2018-02-02 | 2018-09-07 | 东华大学 | A kind of nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode, preparation method and application |
| CN109686972A (en) * | 2018-12-12 | 2019-04-26 | 无锡晶石新型能源股份有限公司 | A kind of preparation method of high magnification hollow sphere lithium nickelate positive electrode |
| CN115433986A (en) * | 2022-10-13 | 2022-12-06 | 盐城工学院 | Method for preparing titanium dioxide nanotube array on spherical titanium particles |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102148359A (en) * | 2010-02-08 | 2011-08-10 | 清华大学 | Preparation method of lithium manganate anode active material |
| CN104157844A (en) * | 2014-08-19 | 2014-11-19 | 哈尔滨工业大学 | High magnifying power lithium-rich manganese-based cathode material with nano/microstructure |
| CN104362291A (en) * | 2014-10-17 | 2015-02-18 | 安徽理工大学 | Lithium-rich cathode material for lithium ion battery, preparation method for lithium-rich cathode material and lithium ion battery |
| CN104692468A (en) * | 2015-03-06 | 2015-06-10 | 华北电力大学 | Preparation method of three-dimensional multiwall hollow sphere NiO nano material |
| CN105977462A (en) * | 2016-06-01 | 2016-09-28 | 中物院成都科学技术发展中心 | Preparation method of lithium-rich manganese-based positive electrode material with hollow structure |
-
2017
- 2017-02-16 CN CN201710084879.6A patent/CN106784740B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102148359A (en) * | 2010-02-08 | 2011-08-10 | 清华大学 | Preparation method of lithium manganate anode active material |
| CN104157844A (en) * | 2014-08-19 | 2014-11-19 | 哈尔滨工业大学 | High magnifying power lithium-rich manganese-based cathode material with nano/microstructure |
| CN104362291A (en) * | 2014-10-17 | 2015-02-18 | 安徽理工大学 | Lithium-rich cathode material for lithium ion battery, preparation method for lithium-rich cathode material and lithium ion battery |
| CN104692468A (en) * | 2015-03-06 | 2015-06-10 | 华北电力大学 | Preparation method of three-dimensional multiwall hollow sphere NiO nano material |
| CN105977462A (en) * | 2016-06-01 | 2016-09-28 | 中物院成都科学技术发展中心 | Preparation method of lithium-rich manganese-based positive electrode material with hollow structure |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108511701A (en) * | 2018-02-02 | 2018-09-07 | 东华大学 | A kind of nickel cobalt sulphur hollow ball as lithium-sulphur cell positive electrode, preparation method and application |
| CN108511701B (en) * | 2018-02-02 | 2020-08-11 | 东华大学 | Nickel-cobalt-sulfur hollow sphere used as positive electrode of lithium-sulfur battery, and preparation method and application thereof |
| CN109686972A (en) * | 2018-12-12 | 2019-04-26 | 无锡晶石新型能源股份有限公司 | A kind of preparation method of high magnification hollow sphere lithium nickelate positive electrode |
| CN115433986A (en) * | 2022-10-13 | 2022-12-06 | 盐城工学院 | Method for preparing titanium dioxide nanotube array on spherical titanium particles |
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