CN103956477B - A kind of preparation method of rich lithium ternary compound potassium ion battery plus plate material - Google Patents
A kind of preparation method of rich lithium ternary compound potassium ion battery plus plate material Download PDFInfo
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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
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- 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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- 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
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- 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
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Abstract
The present invention discloses the preparation method of a kind of rich lithium ternary compound potassium ion battery plus plate material, and described rich lithium ternary compound potassium ion battery plus plate material molecular formula is Li1.2Ni0.13Co0.13Mn0.54O2.First organic precipitant water bath with thermostatic control stirring is dissolved in organic solvent and obtains solution 1 by its preparation method；Then the cobalt salt of solubility, nickel salt, manganese salt and lithium salts ultrasonic dissolution are obtained solution 2 in deionized water；Then solution 2 is at the uniform velocity added drop-wise in solution 1, control to react at temperature 40 80 DEG C after 2 4h in 100 120 DEG C of drying, gained pressed powder is in high-temperature tubular furnace system, stage cools to room temperature with the furnace and i.e. obtains having preferable chemical property after heating up and calcining, granule is uniform, and shape characteristic is spherical or the rich lithium ternary compound potassium ion battery plus plate material of elliposoidal.Its preparation technology is relatively easy, is suitable to industrial large-scale production.
Description
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, be specifically related to a kind of rich lithium tri compound lithium from
The Li of sub-cell positive material1.2Ni0.13Co0.13Mn0.54O2Preparation method.
Background technology
From business-like positive pole material of lithium cobalt acid (LiCoO2) since development[1], owing to its material self-capacity is only its reason
50% (140mAh/g) of opinion capacity, adds that cobalt resource is deficient and problem of environmental pollution, and scholars deepens continuously research, one-tenth
Merit is also prepared for other transiting metal oxidation positive electrodes, such as LiMn2O4 (LiMnO2), LiFePO4 (LiFePO4) etc.[2-3], but
It is relatively low specific energy or power becomes the shortcoming that this kind of material is the most fatal, hinder the further development of the two material.
China proposes to reach for 2015 the energy requirement of 230Wh/kg on space power is applied, additionally at New-energy electric vehicle with dynamic
On power battery, China and Japan etc. have formulated specific energy and have been higher than the target of 200Wh/kg at the year two thousand twenty.Complete these batteries
Referring to, the specific capacity positive electrode higher than more than 220mAh/g is developed into the task of top priority.
In the anode material for lithium-ion batteries of novel research and development, a kind of by Li2MnO3With stratiform LiMO2(M=Mn, Ni,
Co) the stratiform richness lithium ternary compound potassium ion battery plus plate material xLi formed2MnO3-(1-x)LiMO2, owing to exceeding
The specific energy of 250mAh/g, becomes positive electrode of future generation and causes and pay close attention to widely.This material is except having substantially in specific capacity
Outside advantage, safety, production cost are also superior to existing positive electrode.
At present, that rich lithium ternary compound potassium ion battery plus plate material research is more is Li1.2Ni0.13Co0.13Mn0.54O2 [4], coprecipitation is to study one of a kind of most method of this material at present, has synthesis reaction temperature low, and metering ratio is accurate,
The features such as product granularity, pattern are easily controllable.But the method complex process, needs strictly to control to react (gas shield, pH
Value, ammonia volume, reaction temperature, mixing speed etc.), it is precipitated and also needs long time aging, repeatedly sucking filtration cleaning, dry, then
With lithium salts ground and mixed.The method step is many and loaded down with trivial details, significantly increases and decreases production cost.Fan Yongli, science and technology group of China Electronics is public
Taking charge of the 18th institute, application number 200610130302.6, using NaOH as precipitant, NH3•H2O is as chelating agent, by control
Reaction condition processed (pH value, ammonia volume, reaction temperature, mixing speed etc.) obtains Ni, Co, Mn and is co-precipitated presoma,
Complicated process of preparation, can not meet rich lithium ternary compound potassium ion battery plus plate material application needs in field of batteries, difficult
With industrialized production.
List of references
[1]T. Belin, F. Epron, Mater. Sci. Eng. 119 (2005) 105.
[2]B. Lin, Z. Wen, J. Han, X. Wu, Solid State Ionics 179 (2008) 1750.
[3]C. Deng, S. Zhang, B.L. Fu, S.Y. Yang, L. Ma, J. Alloys Compd. 496
(2010) 521.
[4]N. Yabuuchi, K. Yoshii, S.-T. Myung, I. Nakai, S. Komaba, J. Am.
Chem. Soc. 133 (2011) 4404。
Summary of the invention
The invention aims to solve the technical problems such as above-mentioned complicated process of preparation and a kind of rich lithium ternary is provided
The preparation method of anode material for compound lithium ion battery, it is relatively easy that this preparation method has technique, and to producing, equipment requirements is low
And prepare the electrochemical performance of rich lithium ternary compound potassium ion battery plus plate material.
The know-why of the present invention
Organic precipitant water bath with thermostatic control stirring is dissolved in ethanol by the present invention, and additionally by cobalt salt, nickel salt, manganese salt and lithium salts surpass
Sound is dissolved in deionized water；Then solution in the latter is at the uniform velocity added drop-wise in the former organic deposition agent solution, after reaction 3h, control
Temperature processed is 100-120 DEG C and carries out drying and obtain pressed powder.The most i.e. ensure that transition metal acetate molecule in the liquid phase
With being thoroughly mixed of organic precipitant atomic level, ensure that again lithium salts adds together with transition metal salt simultaneously, need not regulate PH
And sucking filtration, hybrid reaction obtains homogeneous precipitation, and prepares rich lithium ternary compound potassium ion battery plus plate by solid sintering technology
Material Li1.2Ni0.13Co0.13Mn0.54O2。
Cobalt method of the present invention is compared with traditional co-precipitation method, prepared by the present invention used organic deposition agent method,
Being precipitated evenly, technique is simple, it is easy to commercial application, has higher economic worth.
Technical scheme
A kind of preparation method of rich lithium ternary compound potassium ion battery plus plate material, described rich lithium ternary compound potassium ion
Cell positive material contains Li, Ni, Co, Mn and O element, and its molecular formula is Li1.2Ni0.13Co0.13Mn0.54O2。
The preparation method of above-mentioned a kind of rich lithium ternary compound potassium ion battery plus plate material, i.e. uses Cobalt
Method, specifically includes following steps:
(1), organic precipitant water bath with thermostatic control stirring is dissolved in organic solvent, obtains solution 1；
Described organic precipitant is selected from 8-hydroxyquinoline or 8-hydroxyquinoline derivant；
Described organic solvent is one or more of ethanol, acetone, chloroform, benzene or diluted acid；
(2), by the cobalt salt of solubility, nickel salt, manganese salt and lithium salts ultrasonic dissolution in deionized water, solution 2 is obtained；
(3), step (2) gained solution 2 is at the uniform velocity added drop-wise in the solution 1 of step (1) gained, controls temperature 40-80 DEG C,
Rotating speed be react 2-4h under the conditions of 400-600r/min after to control temperature again be 100-120 DEG C of drying, gained pressed powder is at height
In temperature tube furnace system, controlling heating rate is that 2-10 DEG C/min is warming up to 200 DEG C of insulation 2-4h, controls heating rate the most again
Being warming up to 400-500 DEG C of precalcining 4-6h for 2-10 DEG C/min, then controlling heating rate is that 2-10 DEG C/min is warming up to 800-
900 DEG C of calcining 6-18h, cool to room temperature with the furnace and i.e. obtain rich lithium ternary compound potassium ion battery plus plate material.
The preparation method of above-mentioned a kind of rich lithium ternary compound potassium ion battery plus plate material
Li1.2Ni0.13Co0.13Mn0.54O2Preparation method, specifically include following steps:
(1), by organic precipitant and organic solvent in organic precipitant: organic solvent is that the ratio of 0.5-5mol:1L is entered
Row mixing, under the conditions of then control rotating speed is 400-600r/min, temperature is 40-80 DEG C, stirring and dissolving obtains solution 1；
Described organic precipitant is 8-hydroxyquinoline or 8-hydroxyquinoline derivant；
Described organic solvent is one or more of ethanol, acetone, chloroform, benzene or diluted acid；
(2), the cobalt salt of solubility, nickel salt, manganese salt and lithium salts are pressed the cobalt salt of solubility, nickel salt, manganese salt with deionized water
Integral molar quantity with lithium salts: deionized water be dissolve under ultrasound condition after the ratio of 0.5-5mol:1L mixes obtain molten
Liquid 2；
The cobalt salt of described solubility, nickel salt, manganese salt and the amount of lithium salts, calculate, i.e. lithium salts: nickel salt: cobalt salt in molar ratio:
In manganese salt, metal ion ratio is 1.2:0.13:0.13:0.54；
The cobalt salt of described solubility be in cobaltous sulfate, cobalt nitrate, cobalt acetate one or more compound；
The nickel salt of solubility be in nickel sulfate, nickel nitrate, nickel acetate one or more compound；
The manganese salt of solubility be in manganese sulfate, manganese nitrate, manganese acetate one or more compound；
The lithium salts of solubility be in lithium carbonate, Lithium hydrate, Quilonorm (SKB) one or more compound；
(3), the solution 2 of step (2) gained controlling drop rate is that 0.1-20ml/min is at the uniform velocity added drop-wise to step (1) institute
Solution 1 in, control temperature 40-80 DEG C under water bath condition, rotating speed be react 2-4h under the conditions of 400-600r/min after control
Temperature is 100-120 DEG C of drying, obtains yellow solid powder；
Above-mentioned solution 2 and the consumption of solution 1, the organic precipitant by solution 1: soluble cobalt, nickel salt in solution 2,
Manganese salt and lithium salts are 0.1-10mol:1mol；
(4), being placed in high-temperature tubular furnace system by the yellow solid powder of step (3) gained, control heating rate is 2-
The ramp of 10 DEG C/min, to 200 DEG C of insulation 2-4h, controls ramp that heating rate is 2-10 DEG C/min extremely the most again
400-500 DEG C of precalcining 4-6h, then controls the ramp that heating rate is 2-10 DEG C/min and calcines 6-to 800-900 DEG C
18h, cools to room temperature with the furnace and i.e. obtains rich lithium ternary compound potassium ion battery plus plate material Li1.2Ni0.13Co0.13Mn0.54O2。
Beneficial effects of the present invention
The preparation method of a kind of rich lithium ternary compound potassium ion battery plus plate material of the present invention, the present invention uses organic molten
Agent as precipitant, in preparation process ionizable metal salt in the liquid phase with being thoroughly mixed, simultaneously of organic solvent atomic level
Lithium salts and cobalt salt, nickel salt, manganese salt adds together, need not regulate pH, ageing, sucking filtration cleaning, and therefore preparation method is simple, is suitable to produce
Industry scale, has higher economic worth.
The final rich lithium ternary compound potassium ion battery plus plate material grain diameter obtained is little, it is easy to sintering, produces after sintering
Thing is uniform, and particle diameter distribution is homogeneous, and has preferable battery performance and chemical property.
Accompanying drawing explanation
Fig. 1, the XRD figure of rich lithium ternary compound potassium ion battery plus plate material of embodiment 1 gained；
Fig. 2, the rich lithium ternary compound potassium ion battery plus plate material SEM figure of embodiment 1 gained；
Fig. 3, the rich lithium ternary compound potassium ion battery plus plate material cycle performance under 0.5C multiplying power of embodiment 1 gained
Curve chart；
Fig. 4, embodiment 1 gained rich lithium ternary compound potassium ion battery plus plate material under 0.5C multiplying power first with 50
Secondary charging and discharging curve；
Fig. 5, the rich lithium ternary compound potassium ion battery plus plate material cyclicity under different multiplying of embodiment 1 gained
Can curve chart.
Detailed description of the invention
Below by specific embodiment and combine accompanying drawing the present invention is expanded on further, but it is not limiting as the present invention.
Embodiment 1
A kind of preparation method of rich lithium ternary compound potassium ion battery plus plate material, described rich lithium ternary compound potassium ion
Cell positive material contains Li, Ni, Co, Mn and O element, and its molecular formula is Li1.2Ni0.13Co0.13Mn0.54O2。
The preparation method of above-mentioned a kind of rich lithium ternary compound potassium ion battery plus plate material, specifically includes following steps:
(1), by 6.3870g(excess 1%) organic precipitant and 55ml organic solvent be by organic precipitant: organic solvent is
The ratio of 1mol:1L mixes, and under the conditions of then control rotating speed is 500r/min, temperature is 80 DEG C, stirring and dissolving obtains solution 1；
Described organic precipitant is 8-hydroxyquinoline；
Described organic solvent is ethanol；
(2), by the 1.6190g cobalt salt of solubility, 1.6176g nickel salt, 6.61742g manganese salt and 6.4273g lithium salts and 50
Ml deionized water presses the cobalt salt of solubility, nickel salt, manganese salt and the integral molar quantity of lithium salts: deionized water is that the ratio of 1mol:1L is entered
Under ultrasonic 20min, solution 2 is obtained after row mixing；
The cobalt salt of described solubility, nickel salt, manganese salt and the amount of lithium salts, calculate, i.e. lithium salts: nickel salt: cobalt salt in molar ratio:
In manganese salt, metal ion ratio is 1.2:0.13:0.13:0.54；
The cobalt salt of described solubility is cobalt acetate；
The nickel salt of solubility is nickel acetate；
The manganese salt of solubility is manganese acetate；
The lithium salts of solubility is Quilonorm (SKB)；
(3), the solution 2 of step (2) gained controlling drop rate is that 0.1ml/min is at the uniform velocity added drop-wise to step (1) gained
Solution 1 in, control temperature 80 DEG C under water bath condition, rotating speed be react 3h under the conditions of 500r/min after to control temperature be 120 DEG C
Dry, obtain yellow solid powder；
Above-mentioned solution 2 and the consumption of solution 1, the organic precipitant 8-hydroxyquinoline by solution 1: solubility in solution 2
Cobalt salt, nickel salt, manganese salt and lithium salts are 1mol:1mol；
(4), being placed in high-temperature tubular furnace system by the yellow solid powder of step (3) gained, controlling heating rate is 5
DEG C/ramp of min to 200 DEG C of insulation 2h, control the ramp that heating rate is 5 DEG C/min more pre-to 500 DEG C
Calcining 4h, then controls the ramp that heating rate is 5 DEG C/min and calcines 12h to 900 DEG C, cool to room temperature with the furnace and i.e. obtain rich
Lithium ternary compound potassium ion battery plus plate material Li1.2Ni0.13Co0.13Mn0.54O2。
By the rich lithium ternary compound potassium ion battery plus plate material Li of above-mentioned gained1.2Ni0.13Co0.13Mn0.54O2X is utilized to penetrate
Line diffractometer is scanned, result as it is shown in figure 1, from figure 1 it appears that its to go out peak sharp-pointed, (006)/(012) and
(108) it is obvious that peak is split in/(110), (003) ratio I to (104) peak strength(003)/I(104)More than 1.2, it is indicated above reality
Execute the rich lithium ternary compound potassium ion battery plus plate material Li of example 1 gained1.2Ni0.13Co0.13Mn0.54O2There is good stratiform knot
Structure.
The rich lithium ternary compound potassium ion battery plus plate material Li of above-mentioned gained1.2Ni0.13Co0.13Mn0.54O2Pass through transmission
Ultramicroscope is observed, and the SEM that it obtains under amplification is 15000 times schemes as shown in Figure 2, figure it is seen that
Above-mentioned gained richness lithium ternary compound potassium ion battery plus plate material Li1.2Ni0.13Co0.13Mn0.54O2Pattern be the most all spherical
Or elliposoidal particle diameter is little, granular size ratio is more uniform, and particle diameter distribution is homogeneous.
By the rich lithium ternary compound potassium ion battery plus plate material Li of above-mentioned gained1.2Ni0.13Co0.13Mn0.54O2It is assembled into
Battery, number of assembling steps is as follows:
1, the preparation of anode pole piece
By above-mentioned gained richness lithium ternary compound potassium ion battery plus plate material Li1.2Ni0.13Co0.13Mn0.54O2, conductive carbon black
It is the ratio mixing of 80:10:10 in mass ratio with bonding polyvinylidene fluoride (PVDF), is subsequently placed on magnetic stirring apparatus stirring
Uniformly slurry, is spread evenly across on aluminium foil, after 120 DEG C of vacuum drying 3h, makes the circular anode pole piece of a diameter of 14mm；
2, the preparation of battery cathode
Scraping off high-purity lithium sheet surface oxide layer in dry glove box, the metal surface exposing gloss i.e. obtains electric
Pond negative pole；
3, experimental button cell assembles
CR2016 type button cell it is assembled in the vacuum glove box of full argon.Electrolyte is LiPF6/ ethylene carbonate
Ester (EC)+dimethyl carbonate (DMC) (volume ratio is 1:1), metal lithium sheet is battery cathode, and barrier film is Celgard2400 poly-third
Alkene thin film.In CR2016 type Snap-type cell positive shell, put into anode pole piece, barrier film is covered on anode pole piece, dropping electrolysis
After liquid, then metal lithium sheet i.e. battery cathode is placed on barrier film gently, places into the nickel foam as backing material, battery is born
Pole cap is on anode cover, and then is assembled into experimental button cell.
The rich lithium ternary compound potassium ion battery plus plate material Li of embodiment 1 gained1.2Ni0.13Co0.13Mn0.54O2Battery
Performance, by the CR2016 type button cell after assembling, is tested on LAND battery test system CT2001A, uses
The multiplying power condition of 0.5C, 1C and 2C is tested respectively.Test result is as shown in Fig. 3, Fig. 4 and Fig. 5.
Fig. 3 is the rich lithium ternary compound potassium ion battery plus plate material Li of embodiment 11.2Ni0.13Co0.13Mn0.54O2It is assembled into
After experimental button cell, front 50 charging and discharging capacities under 0.5C multiplying power and cycle efficieny curve.Can draw from Fig. 3,
The anode material for lithium-ion batteries charge and discharge specific volume first of the ternary manganio richness lithium of embodiment 1 gained under the conditions of 0.5C discharge and recharge
Amount is respectively 311.8mAh/g and 237.1mAh/g, and coulombic efficiency is 76.0% first, and from the beginning of second time, efficiency for charge-discharge is equal
Reach more than 98.0%.
Fig. 4 is after the rich lithium ternary compound potassium ion battery plus plate material of embodiment 1 gained is assembled into experimental button cell
The first with 50th charging and discharging curve figure under 0.5 C multiplying power.In Fig. 41 is charging curve first, 2 be the song that discharges first
Line, 3 be the 50th charging curve, 4 be the 50th discharge curve.Figure 4, it is seen that embodiment 1 gained richness lithium ternary is multiple
Closing anode material for lithium-ion batteries and there is obvious 4.5V high-voltage charge platform, after 50 discharge and recharges, specific discharge capacity is
188.4mAh/g, coulombic efficiency is 99.3%.It is indicated above that the rich lithium ternary compound potassium ion battery plus plate material of the present invention
Li1.13Ni0.20Co0.20Mn0.47O2Battery performance good.
Fig. 5 is after the rich lithium ternary compound potassium ion battery plus plate material of embodiment 1 gained is assembled into experimental button cell
Front 50 specific discharge capacity curves under 1 C and 2C multiplying power, a in Fig. 5 represents front 100 discharge curves, b under 1C multiplying power
Represent front 1000 discharge curves under 2C multiplying power.From figure 5 it can be seen that under 1C multiplying power during electric discharge, the highest electric discharge specific volume
Amount is 203.6mAh/g, and 100 averaged discharge specific capacities are 174.2mAh/g, under 2C multiplying power during electric discharge, and the highest electric discharge specific volume
Amount is 178.1mAh/g, and 100 averaged discharge specific capacities are 155.7mAh/g.It is indicated above that the rich lithium tri compound of the present invention
Anode material for lithium-ion batteries, under the conditions of high magnification, shows the battery performance of excellence.
Embodiment 2
A kind of preparation method of rich lithium ternary compound potassium ion battery plus plate material, described rich lithium ternary compound potassium ion
Cell positive material contains Li, Ni, Co, Mn and O element, and its molecular formula is Li1.2Ni0.13Co0.13Mn0.54O2。
The preparation method of above-mentioned a kind of rich lithium ternary compound potassium ion battery plus plate material, i.e. uses Cobalt
Method, specifically includes following steps:
(1), by organic precipitant and organic solvent in organic precipitant: organic solvent is that the ratio of 0.5mol:1L is carried out
Mixing, under the conditions of then control rotating speed is 400r/min, temperature is 40 DEG C, stirring and dissolving obtains solution 1；
Described organic precipitant is 8-hydroxyquinoline；
Described organic solvent is ethanol；
(2), by the cobalt salt of solubility, nickel salt, manganese salt and lithium salts and deionized water, by the cobalt salt of solubility, nickel salt, manganese salt
Integral molar quantity with lithium salts: deionized water is to obtain solution 2 under ultrasonic 20min after the ratio of 0.5mol:1L mixes；
The cobalt salt of described solubility, nickel salt, manganese salt and the amount of lithium salts, calculate, i.e. lithium salts: nickel salt: cobalt salt in molar ratio:
In manganese salt, metal ion ratio is 1.2:0.13:0.13:0.54；
The cobalt salt of described solubility is cobalt acetate；
The nickel salt of solubility is nickel acetate；
The manganese salt of solubility is manganese acetate；
The lithium salts of solubility is Quilonorm (SKB)；
(3), the solution 2 of step (2) gained controlling drop rate is that 0.1ml/min is at the uniform velocity added drop-wise to step (1) gained
Solution 1 in, control temperature 40 DEG C under water bath condition, rotating speed be react 2h under the conditions of 400r/min after to control temperature be 120 DEG C
Dry, obtain yellow solid powder；
Above-mentioned solution 2 and the consumption of solution 1, the organic precipitant by solution 1: soluble cobalt, nickel salt in solution 2,
Manganese salt and lithium salts are 0.1mol:1mol；
(4), being placed in high-temperature tubular furnace system by the yellow solid powder of step (3) gained, controlling heating rate is 5
DEG C/ramp of min to 200 DEG C of insulation 2h, control the ramp that heating rate is 5 DEG C/min more pre-to 400 DEG C
Calcining 6h, then controls the ramp that heating rate is 5 DEG C/min and calcines 6h to 900 DEG C, cool to room temperature with the furnace and i.e. obtain rich
Lithium ternary compound potassium ion battery plus plate material Li1.2Ni0.13Co0.13Mn0.54O2。
Embodiment 3
A kind of preparation method of rich lithium ternary compound potassium ion battery plus plate material, described rich lithium ternary compound potassium ion
Cell positive material contains Li, Ni, Co, Mn and O element, and its molecular formula is Li1.2Ni0.13Co0.13Mn0.54O2。
The preparation method of above-mentioned a kind of rich lithium ternary compound potassium ion battery plus plate material, i.e. uses Cobalt
Method, specifically includes following steps:
(1), by organic precipitant and organic solvent in organic precipitant: organic solvent is that the ratio of 2.5mol:1L is carried out
Mixing, under the conditions of then control rotating speed is 500r/min, temperature is 60 DEG C, stirring and dissolving obtains solution 1；
Described organic precipitant is 8-hydroxyquinoline；
Described organic solvent is ethanol；
(2), by the cobalt salt of solubility, nickel salt, manganese salt and lithium salts and deionized water, by the cobalt salt of solubility, nickel salt, manganese salt
Integral molar quantity with lithium salts: deionized water is to obtain solution 2 under ultrasonic 20min after the ratio of 2.5mol:1L mixes；
The cobalt salt of described solubility, nickel salt, manganese salt and the amount of lithium salts, calculate, i.e. lithium salts: nickel salt: cobalt salt in molar ratio:
In manganese salt, metal ion ratio is 1.2:0.13:0.13:0.54；
The cobalt salt of described solubility is cobalt acetate；
The nickel salt of solubility is nickel acetate；
The manganese salt of solubility is manganese acetate；
The lithium salts of solubility is Quilonorm (SKB)；
(3), the solution 2 of step (2) gained controlling drop rate is that 10ml/min is at the uniform velocity added drop-wise to step (1) gained
In solution 1, under water bath condition, control temperature 60 C, rotating speed be react 3h under the conditions of 500r/min after to control temperature be 120 DEG C of bakings
Dry, obtain yellow solid powder；
Above-mentioned solution 2 and the consumption of solution 1, the organic precipitant by solution 1: the cobalt salt of solubility, nickel in solution 2
Salt, manganese salt and lithium salts are 5mol:1mol；
(4), being placed in high-temperature tubular furnace system by the yellow solid powder of step (3) gained, controlling heating rate is 5
DEG C/ramp of min to 200 DEG C of insulation 2h, control the ramp that heating rate is 5 DEG C/min more pre-to 500 DEG C
Calcining 4h, then controls the ramp that heating rate is 5 DEG C/min and calcines 12h to 900 DEG C, cool to room temperature with the furnace and i.e. obtain rich
Lithium ternary compound potassium ion battery plus plate material Li1.2Ni0.13Co0.13Mn0.54O2。
Embodiment 4
A kind of preparation method of rich lithium ternary compound potassium ion battery plus plate material, described rich lithium ternary compound potassium ion
Cell positive material contains Li, Ni, Co, Mn and O element, and its molecular formula is Li1.2Ni0.13Co0.13Mn0.54O2。
The preparation method of above-mentioned a kind of rich lithium ternary compound potassium ion battery plus plate material, i.e. uses Cobalt
Method, specifically includes following steps:
(1), by organic precipitant and organic solvent in organic precipitant: organic solvent is that the ratio of 5mol:1L is mixed
Closing, under the conditions of then control rotating speed is 600r/min, temperature is 80 DEG C, stirring and dissolving obtains solution 1；
Described organic precipitant is 8-hydroxyquinoline；
Described organic solvent is ethanol；
(2), by the cobalt salt of solubility, nickel salt, manganese salt and lithium salts and deionized water, by the cobalt salt of solubility, nickel salt, manganese salt
Integral molar quantity with lithium salts: deionized water is to obtain solution 2 under ultrasonic 20min after the ratio of 5mol:1L mixes；
The cobalt salt of described solubility, nickel salt, manganese salt and the amount of lithium salts, calculate, i.e. lithium salts: nickel salt: cobalt salt in molar ratio:
In manganese salt, metal ion ratio is 1.2:0.13:0.13:0.54；
The cobalt salt of described solubility is cobalt acetate；
The nickel salt of solubility is nickel acetate；
The manganese salt of solubility is manganese acetate；
The lithium salts of solubility is Quilonorm (SKB)；
(3), the solution 2 of step (2) gained controlling drop rate is that 20ml/min is at the uniform velocity added drop-wise to step (1) gained
In solution 1, under water bath condition, control temperature 80 DEG C, rotating speed be react 4h under the conditions of 600r/min after to control temperature be 120 DEG C of bakings
Dry, obtain yellow solid powder；
Above-mentioned solution 2 and the consumption of solution 1, the organic precipitant by solution 1: the cobalt salt of solubility, nickel in solution 2
Salt, manganese salt and lithium salts are 10mol:1mol；
(4), being placed in high-temperature tubular furnace system by the yellow solid powder of step (3) gained, controlling heating rate is 5
DEG C/ramp of min to 200 DEG C of insulation 2h, control the ramp that heating rate is 5 DEG C/min more pre-to 500 DEG C
Calcining 4h, then controls the ramp that heating rate is 5 DEG C/min and calcines 18h to 900 DEG C, cool to room temperature with the furnace and i.e. obtain rich
Lithium ternary compound potassium ion battery plus plate material Li1.2Ni0.13Co0.13Mn0.54O2。
In sum, a kind of rich lithium ternary compound potassium ion battery plus plate material that the present invention provides has that capacity is big, follows
Ring performance is good, and production cost is low, it is simple to industrial-scale production etc..Further, rich lithium ternary compound potassium ion battery plus plate material
Material has preferable battery performance and chemical property, and the development to lithium ion battery has great practical significance and society's valency
Value, the development to China's New Energy Industry has good impetus.
The above is only the citing of embodiments of the present invention, it is noted that for the ordinary skill of the art
For personnel, on the premise of without departing from the technology of the present invention principle, it is also possible to make some improvement and modification, these improve and become
Type also should be regarded as protection scope of the present invention.
Claims (6)
1. a preparation method for rich lithium ternary compound potassium ion battery plus plate material, described rich lithium ternary compound potassium ion electricity
Pond positive electrode contains Li, Ni, Co, Mn and O element, and its molecular formula is Li1.2Ni0.13Co0.13Mn0.54O2, it is characterised in that tool
Body comprises the following steps:
(1), organic precipitant water bath with thermostatic control stirring is dissolved in organic solvent, obtains solution 1；
Described organic precipitant is 8-hydroxyquinoline or 8-hydroxyquinoline derivant；
Described organic solvent is one or more of ethanol, acetone, chloroform, benzene or diluted acid；
Described solution 1 is by organic precipitant and organic solvent by organic precipitant: organic solvent is the ratio of 0.5-5mol:1L
Example mixes, and under the conditions of then control rotating speed is 400-600r/min, temperature is 40-80 DEG C, stirring and dissolving obtains；
(2), by the cobalt salt of solubility, nickel salt, manganese salt and lithium salts ultrasonic dissolution in deionized water, solution 2 is obtained；
(3), step (2) gained solution 2 is at the uniform velocity added drop-wise in the solution 1 of step (1) gained, controls temperature 40-80 DEG C, rotating speed
Being 100-120 DEG C of drying for controlling temperature again after reacting 2-4h under the conditions of 400-600r/min, gained pressed powder is at high-temperature pipe
In formula furnace system, controlling heating rate is that 2-10 DEG C/min is warming up to 200 DEG C of insulation 2-4h, and controlling heating rate the most again is 2-
10 DEG C/min is warming up to 400-500 DEG C of precalcining 4-6h, and then controlling heating rate is that 2-10 DEG C/min is warming up to 800-900 DEG C
Calcining 6-18h, cools to room temperature with the furnace and i.e. obtains rich lithium ternary compound potassium ion battery plus plate material；
Above-mentioned solution 2 and the consumption of solution 1, the organic precipitant by solution 1: soluble cobalt, nickel salt in solution 2, manganese salt
It is 0.1-10mol:1mol with lithium salts.
2. the preparation method of rich lithium ternary compound potassium ion battery plus plate material as claimed in claim 1
Li1.2Ni0.13Co0.13Mn0.54O2Preparation method, it is characterised in that the organic precipitant described in step (1) is 8-hydroxyquinoline；
Described organic solvent is ethanol.
3. the preparation method of rich lithium ternary compound potassium ion battery plus plate material as claimed in claim 2
Li1.2Ni0.13Co0.13Mn0.54O2Preparation method, it is characterised in that the solution 2 described in step (2) be by the cobalt salt of solubility,
Nickel salt, manganese salt and lithium salts and deionized water are by the cobalt salt of solubility, nickel salt, manganese salt and the integral molar quantity of lithium salts: deionization water body
Amass to dissolve under ultrasound condition after the ratio for 0.5-5mol:1L mixes and obtain；
The cobalt salt of described solubility, nickel salt, manganese salt and the amount of lithium salts, calculate, i.e. lithium salts: nickel salt: cobalt salt in molar ratio: manganese salt
Middle metal ion ratio is 1.2:0.13:0.13:0.54；
The cobalt salt of described solubility be in cobaltous sulfate, cobalt nitrate, cobalt acetate one or more compound；
The nickel salt of solubility be in nickel sulfate, nickel nitrate, nickel acetate one or more compound；
The manganese salt of solubility be in manganese sulfate, manganese nitrate, manganese acetate one or more compound；
The lithium salts of solubility be in lithium carbonate, Lithium hydrate, Quilonorm (SKB) one or more compound.
4. the preparation method of rich lithium ternary compound potassium ion battery plus plate material as claimed in claim 3
Li1.2Ni0.13Co0.13Mn0.54O2Preparation method, it is characterised in that the cobalt salt of the solubility described in step (2) is cobalt acetate；
The nickel salt of solubility is nickel acetate；
The manganese salt of solubility is manganese acetate；
The lithium salts of solubility is Quilonorm (SKB).
5. the preparation method of rich lithium ternary compound potassium ion battery plus plate material as claimed in claim 4
Li1.2Ni0.13Co0.13Mn0.54O2Preparation method, it is characterised in that the at the uniform velocity dropping described in step (3) i.e. controls drop rate
For 0.1-20ml/min, solution 2 is added drop-wise in solution 1.
6. the preparation method of rich lithium ternary compound potassium ion battery plus plate material as claimed in claim 5
Li1.2Ni0.13Co0.13Mn0.54O2Preparation method, it is characterised in that step (3) control heating rate be that 5 DEG C/min is warming up to
200 DEG C of insulation 2-4h, controlling heating rate the most again is that 5 DEG C/min is warming up to 400-500 DEG C of precalcining 4-6h, then controls to rise
Temperature speed is that 5 DEG C/min is warming up to 900 DEG C of calcining 6-18h.
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| CN104852038B (en) * | 2015-04-08 | 2017-02-01 | 中国科学院长春应用化学研究所 | Preparation method of high-capacity quickly-chargeable/dischargeable lithium ion battery ternary anode material |
| CN104900857A (en) * | 2015-06-02 | 2015-09-09 | 上海电力学院 | Preparation method of trace Mo-doped lamellar lithium-enriched ternary positive electrode material |
| CN104835955B (en) * | 2015-06-02 | 2017-05-31 | 中国东方电气集团有限公司 | A kind of lithium ion battery nickle cobalt lithium manganate composite positive pole and preparation method thereof |
| CN105070902A (en) * | 2015-07-17 | 2015-11-18 | 济南大学 | Mixed transition metal based preparation method for cathode material of sodium secondary battery |
| CN105070905A (en) * | 2015-08-14 | 2015-11-18 | 东莞市迈科科技有限公司 | Layered cathode material of lithium-ion battery and preparation method of layered cathode material |
| CN105185976A (en) * | 2015-08-14 | 2015-12-23 | 东莞市迈科科技有限公司 | Lithium-ion battery cathode material nickel-cobalt lithium aluminate and preparation method thereof |
| CN105185980A (en) * | 2015-08-17 | 2015-12-23 | 上海电力学院 | Preparation method of TiO2-coated layered lithium-rich ternary cathode material |
| CN105742623A (en) * | 2016-04-07 | 2016-07-06 | 华南师范大学 | Nanometer prismatic lithium-rich material and preparation method and application thereof |
| CN108376778A (en) * | 2018-02-27 | 2018-08-07 | 天津丹兴科技有限责任公司 | The method that solvent-thermal method prepares high-performance lithium-rich anode material |
| CN108806996B (en) * | 2018-06-08 | 2019-11-08 | 上海应用技术大学 | It is a kind of using nickel foam as the Ni of matrixxMn1-xCo2O4The preparation method of nano flower |
| CN114497452A (en) * | 2021-12-28 | 2022-05-13 | 高点(深圳)科技有限公司 | Positive electrode material for silicon battery and preparation method and application thereof |
| CN114530584B (en) * | 2022-02-18 | 2024-04-16 | 广州大学 | Polyaniline micron-rod structured lithium-rich manganese-based positive electrode material and preparation method and application thereof |
| CN115947388A (en) * | 2022-12-31 | 2023-04-11 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ternary nano positive electrode material, product and application thereof |
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