CN106602015A - Preparation method for fluorine-doped nickel-cobalt-manganese system ternary positive electrode material and prepared material - Google Patents
Preparation method for fluorine-doped nickel-cobalt-manganese system ternary positive electrode material and prepared material Download PDFInfo
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- CN106602015A CN106602015A CN201611190763.2A CN201611190763A CN106602015A CN 106602015 A CN106602015 A CN 106602015A CN 201611190763 A CN201611190763 A CN 201611190763A CN 106602015 A CN106602015 A CN 106602015A
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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
- H01M4/362—Composites
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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
- 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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- 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
- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a preparation method for a fluorine-doped nickel-cobalt-manganese system ternary positive electrode material. The preparation method comprises the following steps of mixing a transitional metal source water solution, an alkali liquid and ammonium hydroxide, stirring and heating to perform a reaction, and performing aging, filtering, washing and drying on sediments obtained in the reaction to obtain a nickel-cobalt-manganese composite precursor; performing heat treatment on the precursor at a temperature of 500-550 DEG C, then mixing with a lithium source and a fluorine source, then adding a fluxing agent, and mixing and preparing into a blank; and putting the blank into a reaction furnace to be subjected to constant-temperature calcining at a temperature of 700-1,000 DEG C, and then cooling, washing and drying to obtain the fluorine-doped nickel-cobalt-manganese system ternary positive electrode material. The fluorine-doped ternary positive electrode material prepared by the preparation method is uniform in average grain diameter and excellent in cycle performance; and in addition, the preparation method is simple in process, low in production cost, energy-saving and efficient, and suitable for industrial production.
Description
Technical field
The invention belongs to battery material preparation field, is related to a kind of preparation of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped
Method and obtained material, more particularly to a kind of molten-salt growth method prepares the method and system of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped
The material for obtaining.
Background technology
In the positive electrode of lithium ion battery, the cobalt acid lithium (LiCoO of layer structure2), it is rare, high due to cobalt resource
Impact of the expensive price and its toxicity to environment, limits its development potentiality.The anode material nickel of another kind of layer structure
Sour lithium (LiNiO2) although price is relatively low, better performances, prepare complicated and there is high temperature safe sex chromosome mosaicism.By contrast
LiMn2O4 (the LiMn of spinelle2O4) because manganese material is abundant and cheap and nontoxic, pollute little, easy recovery, operating voltage
High, de- lithium amount is big and the advantage such as has a safety feature, and becomes one of most promising electrode material of lithium ion battery of new generation.But
Be spinel lithium manganate specific capacity is low, cycle performance is poor and unstable always its Commercialization application of long-standing problem of high-temperature behavior
Major obstacle.The LiFePO of another kind of olivine structural4Possess good structural stability and cyclicity, raw material source
Extensively, the advantages of cheap and non-environmental-pollution, in power and the big field of energy storage two basic application has been obtained at present, but
Due to its native electronic electrical conductivity relatively low (～10-9S/cm), and lithium ion is smaller in its internal diffusion rate, still have
Certain restriction.LiFePO leading at present4Monomer energy density about 130Wh/kg or so of battery, even if according to
LiFePO4The limit capacitance of material 170mAh/g is calculated, and the energy density of corresponding battery is also only capable of reaching 216Wh/kg, nothing
Method realizes the set developing goal of the year two thousand twenty 350Wh/kg.
At present, the monomer energy density of nickel cobalt manganese systems ternary battery generally reaches 160～180Wh/Kg, LG and three magnitude energy
Enough accomplish more than 200Wh/kg.Although LiFePO4Battery possesses certain excellent in terms of security with circulation energy compared to ternary
Gesture, but with updating that material system and battery management are united, with LiFePO on security circulation energy4Gap is gradually
Reduce.In view of the electric automobile an urgent demand high to energy density, LiFePO4The too low problem of battery energy density is difficult to
To solution, short -board effect is further obvious, and ternary material is the existing unique selection for reaching the year two thousand twenty 350Wh/kg targets.
At present, researcher has done relatively broad research for ternary material, has researched and developed including co-precipitation
Method, sol-gal process and high temperature solid-state method etc., high temperature solid-state method technological process is short, and equipment is simple and is easy to large-scale production, but
Time-consuming for method presence, and energy consumption is big, and batch mixing inequality easily occur, cannot form homogeneous eutectic and each batch quality
Unstable the problems such as, it is difficult to ensure that Ni, Co and Mn each element is evenly distributed in building-up process, simultaneously synthesizing material morphology is not advised
Then, so as to affecting material electrochemical performance.The material of sol-gel process synthesis has specific capacity height and good cycle etc. excellent
Point, but synthesis cycle is long, and the difficulty of industrialized production is larger.Coprecipitation by the suitable precipitating reagent of control, pH value,
The technological parameters such as reaction temperature, reaction time, charging rate and mixing speed have obtained industrial applications, but equally exist work
Skill process complexity, poor repeatability and control condition strictly, can not very well meet to a certain extent lithium ion battery to positive electrode
Requirement.
Molten-salt growth method is just causing extensive concern with its process is simple, the features such as the reaction time is short.Molten-salt growth method synthesis is containing lithium just
Pole material, is generally adopted by such as LiCl, LiNO3、LiCO3, LiOH or LiF these lithium salts, they not only as solvent but also be mesh
Mark product provides lithium source.The Main Function of fused salt is the effect for serving as " solvent " and dispersive medium in whole course of reaction.Instead
Answer raw material typically to have certain solubility in selected salt, therefore reactant can be made to realize atomic scale in the liquid phase
Contact, in addition, reactant has bigger diffusion rate in fused salt, the such as ion mobility in fused salt is 1 × 10-5～1
×10-8cm2/ s, and in solid phase it is only 1 × 10-8cm2/ s, both effects can be realized under short period and lower temperature
React.
Tan et al. (K.S.Tan, M.V.Reddy, G.V.S.Rao, B.Chowdari.J.Power Sources, 2005,
147,241-248) the LiCl-LiNO at 650 DEG C3The LiCoO of 100～500nm has been prepared in mixed salt2Powder, and 850
The large-size powder body material obtained at DEG C, with more preferable stable circulation performance and higher capacity.
Kim et al. (J.H.Kim, S.T.Myung, Y.K.Sun.Electrochim.Acta, 2004,49,219-227) with
MnOOH and Ni (OH)2For presoma, LiCl and LiOH mixed salts, control temperature is selected to synthesize spinelle at 700～900 DEG C
LiM2O4The LiMn of structure1.5Ni0.5O4。
Ni et al. (J.F.Ni, H.H.Zhou, J.T.Chen, X.X.Zhang, Mater.Lett., 2007,61,1260-
1264) first with Li2CO3、FeC2O4And NH4H2PO4For initiation material, react at 450 DEG C, subsequently the KCl again at 750 DEG C melts
Further process in salt, the LiFePO of the olivine structural for obtaining4Ball powders, its capacity reaches 130.3mAh/g.
Chang et al. (Z.Chang, Z.Chen, F.Wu, X.Z.Yuan, H.Wang.Electrochim.Acta, 2009,
54(26):6529-6535.) with LiOH and LiNO3It is that fused-salt medium and lithium source are mixed with the hydroxide of Co, Ni and Mo
Li (Ni1/3Co1/3Mn1/3)O2Positive electrode.
Kimijima et al. (Kimijima T, Zettsu N, Teshima K.Crystal Growth＆Design,
2016.) Li (Ni of octahedral shape are prepared in molten sulfate at 1000 DEG C1/3Co1/3Mn1/3)O2, and point out Na+Ion
Contribute to the generation of the pattern, and Li+Ion presence is more likely to generate the polyhedron for blocking.
However, the preparation method of existing nickel cobalt manganese cathode material still suffers from heating uneven, reaction time and reaction
The problems such as temperature is high, so as to reduce the performance of battery.
The content of the invention
Still suffer from heating uneven, reaction time and reaction temperature for the preparation method of existing nickel cobalt manganese cathode material
Degree is high, the problems such as so as to the performance for reducing battery, the invention provides a kind of molten-salt growth method prepares the nickel cobalt manganese systems three of Fluorin doped
The method of first positive electrode and obtained material.By the average grain of Fluorin doped tertiary cathode material obtained in the method for the invention
Footpath is uniform, and cycle performance is excellent；Also, preparation method process is simple of the present invention, low production cost, efficient energy-saving is suitable for work
Industry metaplasia is produced.
It is that, up to this purpose, the present invention is employed the following technical solutions：
In a first aspect, the invention provides a kind of preparation method of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped, described
Method is comprised the following steps：
(1) aqueous solution of transition metal source, alkali lye and ammoniacal liquor are mixed, stirs and heat and reacted, reaction gained is heavy
Form sediment into it is aged, be filtered, washed and dried after, obtain nickel cobalt manganese composite precursor；
(2) step (1) gained nickel cobalt manganese composite precursor is heat-treated at 500 DEG C～550 DEG C, then with lithium source
With Fluorine source mixing, flux is added, mix and make base substrate；
(3) step (2) base substrate is placed in in reacting furnace the calcining at constant temperature at 700 DEG C～1000 DEG C, then Jing cooling,
Wash and be dried, obtain the nickel cobalt manganese systems tertiary cathode material of Fluorin doped.
Wherein, described in step (2) be heat-treated temperature can for 500 DEG C, 505 DEG C, 510 DEG C, 515 DEG C, 520 DEG C, 525
DEG C, 530 DEG C, 535 DEG C, 540 DEG C, 545 DEG C or 550 DEG C etc., it is not limited to cited numerical value, in the number range other
Unrequited numerical value is equally applicable；Calcining heat described in step (3) can for 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C,
950 DEG C or 1000 DEG C etc., it is not limited to other unrequited numerical value are equally fitted in cited numerical value, the number range
With.
In the present invention, it is this area conventional method that step is aged described in (1), is filtered, washed and dried method, herein not
Repeat again.
The purpose being heat-treated described in step (2) is, by heat treatment, can further to avoid the mixing of cation, it is ensured that
Follow-up good chemical property.
The present invention can guarantee that reactant has larger diffusion rate, so as to ensure that nucleation is equal with fuse salt as reaction medium
One property, and then it is good to be eventually exhibited as the uniformity of material；Meanwhile, the product of different batches can also be made as reaction medium with fuse salt
Product uniformity is guaranteed.
The fluorine adulterated in the present invention has highest electronegativity and very high free energy, by fused salt fluorination treatment technology,
It is favorably improved the energy density and cyclical stability of material.
It is following as currently preferred technical scheme, but not as the present invention provide technical scheme restriction, pass through
Technical scheme below, can preferably reach and realize the technical purpose and beneficial effect of the present invention.
Used as currently preferred technical scheme, transition metal source is nickel in step (1) the transition metal saline solution
Source, cobalt source and manganese source.
Preferably, the nickel source be in nickel sulfate, nickelous carbonate, nickel nitrate or nickel hydroxide any one or at least two
Combination, the combination is typical but non-limiting examples have：The combination of the combination of nickel sulfate and nickelous carbonate, nickelous carbonate and nickel nitrate,
The combination of nickel nitrate and nickel hydroxide, the combination of nickel sulfate, nickelous carbonate and nickel nitrate, nickelous carbonate, nickel nitrate and nickel hydroxide
Combination, combination of nickel sulfate, nickelous carbonate, nickel nitrate and nickel hydroxide etc..
Preferably, the cobalt salt be in cobaltous sulfate, cobalt carbonate, cobalt nitrate or cobalt hydroxide any one or at least two
Combination, the combination is typical but non-limiting examples have：The combination of the combination of cobaltous sulfate and cobalt carbonate, cobalt carbonate and cobalt nitrate,
The combination of cobalt nitrate and cobalt hydroxide, the combination of cobaltous sulfate, cobalt carbonate and cobalt nitrate, cobaltous sulfate, cobalt carbonate, cobalt nitrate and hydrogen-oxygen
Change combination of cobalt etc..
Preferably, the manganese salt be in manganese sulfate, manganese carbonate, manganese nitrate or manganous hydroxide any one or at least two
Combination, the combination is typical but non-limiting examples have：The combination of the combination of manganese sulfate and manganese carbonate, manganese carbonate and manganese nitrate,
The combination of manganese nitrate and manganous hydroxide, the combination of manganese sulfate, manganese carbonate and manganese nitrate, manganese sulfate, manganese carbonate, manganese nitrate and hydrogen-oxygen
Change combination of manganese etc..
As currently preferred technical scheme, nickel ion in step (1) the transition metal saline solution, cobalt ions and
The mol ratio of manganese ion is (1～8):(1～2):(1～3), such as 1:(1～2):(1～3), 2:(1～2):(1～3), 3:(1
～2):(1～3), 4:(1～2):(1～3), 5:(1～2):(1～3), 6:(1～2):(1～3), 7:(1～2):(1～3) or
8:(1～2):(1～3) etc., and for example (1～8):1:(1～3), (1～8):1.3:(1～3), (1～8):1.5:(1～3), (1
～8):1.7:(1～3) or (1～8):2:(1～3) etc., and for example (1～8):(1～2):1st, (1～8):(1～2):1.5th, (1～
8):(1～2):2nd, (1～8):(1～2):2.5 or (1～8):(1～2):3 etc., can also be such as 1:1:1、2:1.3:1.5、4:1.5:
2、6:1.7:2.5 or 8:2:3 etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
Sample is suitable for, preferably (1～6):(1～2):(1～3).
Preferably, in step (1) the transition metal saline solution nickel ion, cobalt ions and manganese ion total ion concentration
For 2mol/L～3mol/L, such as 2mol/L, 2.3mol/L, 2.5mol/L, 2.7mol/L or 3mol/L etc., it is not limited to
Other unrequited numerical value are equally applicable in cited numerical value, the number range, preferably 2mol/L.
In the present invention, the ion concentration in the transition metal saline solution need to be controlled within the specific limits, if ion is dense
Height is spent, dissolving is difficult；If ion concentration is too low, dissolving is not a problem, but in view of actual production, can make production efficiency mistake
It is low, increase cost.
Used as currently preferred technical scheme, alkali lye described in step (1) is NaOH, potassium hydroxide, ammonium carbonate
In sodium carbonate any one or at least two the aqueous solution, combination typical case but non-limiting examples have：NaOH and
The combination of the combination of the combination of potassium hydroxide, potassium hydroxide and ammonium carbonate, ammonium carbonate and sodium carbonate, NaOH, potassium hydroxide,
Combination of ammonium carbonate and sodium carbonate etc..
Preferably, the concentration of step (1) alkali lye is 2mol/L～10mol/L, such as 2mol/L, 3mol/L, 4mol/
L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L etc., it is not limited to cited numerical value, the number
Other unrequited numerical value are equally applicable in the range of value, preferably 2mol/L～5mol/L.
Preferably, the concentration of step (1) ammoniacal liquor is 3mol/L～6mol/L, such as 3mol/L, 4mol/L, 5mol/L
Or 6mol/L etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range, preferably
For 5mol/L.
Used as currently preferred technical scheme, step (1) stirring is mechanical agitation, preferably ultrasonic agitation.
Preferably, step (1) heating-up temperature be 50 DEG C～65 DEG C, such as 50 DEG C, 53 DEG C, 55 DEG C, 57 DEG C, 60 DEG C,
63 DEG C or 65 DEG C etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range, it is excellent
Elect 55 DEG C as.
Preferably, control in step (1) course of reaction reaction system pH be 10～14, such as 10,10.5,11,
11.5th, 12,12.5,13,13.5 or 14 etc., it is not limited to other are unrequited in cited numerical value, the number range
Numerical value is equally applicable, and preferably 11～12.
Preferably, the reaction time of step (1) reaction be 18h～24h, such as 18h, 19h, 20h, 21h, 22h,
23h or 24h etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Preferably, the reaction atmosphere of step (1) reaction is inert atmosphere.
Preferably, the inert atmosphere be helium atmosphere, argon gas atmosphere or neon atmosphere in any one or at least two
Combination, combination typical case but non-limiting examples have：The combination of helium atmosphere and argon gas atmosphere, argon gas atmosphere and neon gas
The combination of atmosphere, combination of helium atmosphere, argon gas atmosphere and neon atmosphere etc..
Used as currently preferred technical scheme, time of step (2) heat treatment is 5h～7h, such as 5h, 5.5h,
6h, 6.5h or 7h etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Preferably, step (2) lithium source be lithium hydroxide, lithium carbonate, lithium nitrate or lithium acetate in any one or extremely
Few two kinds combination, the combination is typical but non-limiting examples have：The combination of lithium hydroxide and lithium carbonate, lithium carbonate and nitric acid
The combination of the combination of lithium, lithium nitrate and lithium acetate, the combination of lithium hydroxide, lithium carbonate and lithium nitrate, lithium hydroxide, lithium carbonate,
Combination of lithium nitrate and lithium acetate etc..
Preferably, the consumption of step (2) lithium source and the ratio of the mole of presoma are (1.0～1.08):1, for example
1:1、1.02:1、1.04:1、1.06:1 or 1.08:1 etc., it is not limited to cited numerical value, in the number range other
Unrequited numerical value is equally applicable.
Preferably, step (2) Fluorine source be lithium fluoride, potassium fluoride or ammonium fluoride in any one or at least two group
Close, the combination is typical but non-limiting examples have：The combination of the combination of lithium fluoride and potassium fluoride, potassium fluoride and ammonium fluoride, fluorine
Change combination of lithium, potassium fluoride and ammonium fluoride etc..
Preferably, it with the ratio of the mole of presoma is (0.05～0.2) that the consumption of step (2) Fluorine source is:1, example
Such as 0.05:1、0.07:1、0.1:1、0.13:1、0.15:1、0.17:1 or 0.2:1 etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range.
Preferably, step (2) flux is the chlorination of chloride, the chloride of sodium, the chloride of potassium or the magnesium of lithium
In thing any one or at least two combination, combination typical case but non-limiting examples have：The chloride of lithium and the chlorine of sodium
Compound, the chloride of sodium and the chloride of potassium, muriatic combination of the chloride of lithium, the chloride of magnesium and potassium etc..
Preferably, the consumption of step (2) flux is 1 times～the 10 of nickel cobalt manganese composite precursor and lithium source gross mass
Times, such as 1 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times or 10 times etc., it is not limited to cited numerical value,
Other unrequited numerical value are equally applicable in the number range.
Preferably, step (2) is described is mixed into mechanical mixture.
Preferably, the mechanical mixture be grind, stir or ball milling in any one or at least two combination, described group
Closing typical case but non-limiting examples has：Grinding and the combination stirred, stirring and the combination of ball milling, the group of grinding, stirring and ball milling
Close etc..
Used as currently preferred technical scheme, reacting furnace described in step (3) is air atmosphere stove.
Preferably, the heating rate in step (3) reacting furnace is 2 DEG C/min～10 DEG C/min, such as 2 DEG C/min, 3
DEG C/min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/min etc., but and not only limit
Other unrequited numerical value are equally applicable in cited numerical value, the number range.
Preferably, the temperature of step (3) calcining at constant temperature is 800 DEG C～900 DEG C.
Preferably, the time of step (3) calcining at constant temperature be 10h～18h, such as 10h, 11h, 12h, 13h, 14h,
15h, 16h, 17h or 18h etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
It is suitable for, preferably 15h～16h.
Preferably, step (3) it is described be cooled to be cooled to 25 DEG C～30 DEG C, i.e. room temperature.
Preferably, step (3) washing is to be washed with deionized.
As currently preferred technical scheme, the method comprising the steps of：
(1) it is (1～6) by the mol ratio of nickel ion, cobalt ions and manganese ion:(1～2):The total ion concentration of (1～3)
It is 5mol/L's for alkali lye and concentration that the aqueous solution of the nickel source of 2mol/L, cobalt source and manganese source, concentration are 2mol/L～5mol/L
Ammoniacal liquor mixes, and being stirred and heated to 55 DEG C carries out under an inert atmosphere reaction 18h～24h, and reaction system is controlled in course of reaction
PH be 11～12, reaction gained precipitate into it is aged, be filtered, washed and dried after, obtain nickel cobalt manganese composite precursor；
(2) step (1) gained nickel cobalt manganese composite precursor is carried out into heat treatment 5h～7h at 500 DEG C～550 DEG C, then
Mix with lithium source and Fluorine source, the consumption of lithium source is (1.0～1.08) with the ratio of the mole of presoma:1, the consumption of Fluorine source with it is front
The ratio for driving the mole of body is (0.05～0.2):1, add 1 times～10 times of nickel cobalt manganese composite precursor and lithium source gross mass
Flux, mix and make base substrate；
(3) step (2) base substrate is placed in reacting furnace with the ramp of 2 DEG C/min～10 DEG C/min, in 800 DEG C
Calcining at constant temperature 15h～16h at～900 DEG C, then Jing coolings, washing and drying, obtain the nickel cobalt manganese systems tertiary cathode of Fluorin doped
Material.
Second aspect, the invention provides the nickel cobalt manganese systems tertiary cathode material of Fluorin doped that above-mentioned preparation method is prepared
Material, the nickel cobalt manganese systems tertiary cathode material of the Fluorin doped is Li1+xNiαCoβMnγFyO2-y, wherein 0≤x≤0.2,0<y≤
0.1,0<α<1,0<β<1,0<γ<1.
Wherein, x can be 0,0.05,0.1,0.15 or 0.2 etc., it is not limited to cited numerical value, the number range
Interior other unrequited numerical value are equally applicable；Y can be 0.01,0.03,0.05,0.07,0.09 or 0.1 etc., it is not limited to
Other unrequited numerical value are equally applicable in cited numerical value, the number range；α can for 0.1,0.2,0.3,0.4,0.5,
0.6th, 0.7,0.8,0.9 or 1 etc., it is not limited to other unrequited numerical value are same in cited numerical value, the number range
Sample is suitable for；β can be 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9 or 1 etc., it is not limited to cited number
Other unrequited numerical value are equally applicable in value, the number range；γ can for 0.1,0.2,0.3,0.4,0.5,0.6,0.7,
0.8th, 0.9 or 1 etc., it is not limited to other unrequited numerical value are equally applicable in cited numerical value, the number range.
Compared with prior art, the invention has the advantages that：
(1) present invention can guarantee that reactant has larger diffusion rate, so as to ensure nucleation with fuse salt as reaction medium
Homogeneity, and then it is good to be eventually exhibited as the uniformity of material；Meanwhile, can also make different batches by reaction medium of fuse salt
Homogeneity of product is guaranteed；
(2) fluorine adulterated in the present invention has highest electronegativity and very high free energy, by fused salt fluorination treatment skill
Art, is favorably improved the energy density and cyclical stability of material, and then makes with full battery obtained in material prepared by the present invention
Charging/discharging voltage scope be 3.0～4.2V, 0.5C first discharge specific capacities can be more than 160mAh/g, circulation 100 times after hold
Amount conservation rate reaches as high as 99%；
(3) average grain diameter of the nickel cobalt manganese systems tertiary cathode material of the obtained Fluorin doped of the present invention is uniform, and cycle performance is excellent
Different, preparation method process is simple, low production cost, efficient energy-saving is suitable for industrialized production.
Description of the drawings
Fig. 1 is the XRD of the nickel cobalt manganese systems tertiary cathode material that the embodiment of the present invention 2 is prepared；
Fig. 2 is the scanning electron microscope (SEM) photograph of the nickel cobalt manganese systems tertiary cathode material that the embodiment of the present invention 2 is prepared；
Fig. 3 is the embodiment of the present invention 2 to be discharged first specific volume with the 0.5C of battery obtained in nickel cobalt manganese systems tertiary cathode material
Spirogram；
Fig. 4 is the embodiment of the present invention 2 to be kept with capacity after circulating battery obtained in nickel cobalt manganese systems tertiary cathode material 100 times
Rate figure.
Specific embodiment
For the present invention is better described, technical scheme is readily appreciated, below to the present invention further specifically
It is bright.But following embodiments is only the simple example of the present invention, the scope of the present invention is not represented or limits, this
Invention protection domain is defined by claims.
Specific embodiment of the invention part provides a kind of preparation method of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped,
The method comprising the steps of：
(1) aqueous solution of transition metal source, alkali lye and ammoniacal liquor are mixed, stirs and heat and reacted, reaction gained is heavy
Form sediment into it is aged, be filtered, washed and dried after, obtain nickel cobalt manganese composite precursor；
(2) step (1) gained nickel cobalt manganese composite precursor is heat-treated at 500 DEG C～550 DEG C, then with lithium source
With Fluorine source mixing, flux is added, mix and make base substrate；
(3) step (2) base substrate is placed in in reacting furnace the calcining at constant temperature at 700 DEG C～1000 DEG C, then Jing cooling,
Wash and be dried, obtain the nickel cobalt manganese systems tertiary cathode material of Fluorin doped.
It is below present invention typical case but non-limiting example：
Embodiment 1：
A kind of preparation method of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped is present embodiments provided, methods described includes
Following steps：
(1) take 100mL ion concentrations be 2.5mol/L nickel, cobalt and manganese sulfate mixed aqueous solution (nickel ion, manganese from
The mol ratio of son and cobalt ions is 5:2:3), it is added in the reactor with agitating device, leads to argon gas, while being slowly added to dense
The ammonia spirit of sodium hydroxide solution and concentration for 5mol/L for 5mol/L is spent, 20h is reacted in 55 DEG C under an inert atmosphere, is adjusted
Section pH is stable 12, Jing filtering with after supersound washing, obtains Ni0.5Co0.2Mn0.3(OH)2Precursor pulp；
(2) Ni for obtaining step (1)0.5Co0.2Mn0.3(OH)2Precursor pulp is heat-treated 6h at 500 DEG C, then presses
LiNi0.5Co0.2Mn0.3O1.85F0.15Stoichiometric proportion weigh lithium hydroxide and lithium fluoride (mol ratio be 25:3) mix, then to
The equimolar potassium chloride and sodium chloride of 10 times of gross mass are wherein added, ball milling mixing is uniform, and prepares base substrate by cake-making machine；
(3) base substrate obtained by step (2) is placed in air atmosphere stove, with the ramp of 5 DEG C/min, in 850 DEG C of perseverances
Temperature calcining 16h, is finally cooled to room temperature, and deionized water is fully washed, the rich lithium tertiary cathode of drying to obtain fluorination treatment
Material LiNi0.5Co0.2Mn0.3O1.85F0.15。
With rich lithium tertiary cathode material LiNi0.5Co0.2Mn0.3O1.85F0.15Prepare full battery：
It is in proportion 96%:1.8%:2.2% weighs respectively LiNi0.5Co0.2Mn0.3O1.85F0.15Positive electrode, Super P
Conductive black and PVDF binding agents, with NMP as solvent, are coated on aluminium foil after being well mixed and make positive plate, and negative plate adopts stone
Ink is active material, and its content is 95.5%, and conductive black is conductive agent, and content is 2%, CMC and SBR is binding agent, and its is total
Measure as 2.5%, with Celgard 2300 as barrier film, the LiPF of 1mol/L6/EC:DMC (volume ratios 1:1) it is electrolyte, is assembled into
063048 box hat battery, its charging/discharging voltage scope is 3.0V～4.2V, and 0.5C first discharge specific capacities are 163.5mAh/g, are followed
Capability retention is 97.6% after ring 100 times.
Embodiment 2：
A kind of preparation method of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped is present embodiments provided, methods described includes
Following steps：
(1) mixed aqueous solution (nickel ion, the manganese ion of the sulfate that 200mL ion concentrations are 2mol/L nickel, cobalt and manganese are taken
It is 1 with the mol ratio of cobalt ions:1:1), it is added in the reactor with agitating device, leads to argon gas, while being slowly added to concentration
Sodium hydroxide solution and concentration for 10mol/L is 5mol/L ammonia spirits, reacts 24h in 50 DEG C under an inert atmosphere, is adjusted
PH is stable 11.5, Jing filtering with after supersound washing, obtains Ni1/3Co1/3Mn1/3(OH)2Precursor pulp；
(2) Ni for obtaining step (1)1/3Co1/3Mn1/3(OH)2Precursor pulp is heat-treated 7h at 550 DEG C, then presses
LiNi1/3Co1/3Mn1/3O1.9F0.1Stoichiometric proportion weigh lithium hydroxide and lithium fluoride (mol ratio be 9:1) mix, then to it
The equimolar potassium chloride of 10 times of middle addition nickel cobalt manganese composite precursor and lithium source gross mass, is mechanically well mixed,
And base substrate is prepared by cake-making machine；
(3) base substrate obtained by step (2) is placed in air atmosphere stove, with the ramp of 2 DEG C/min, in 900 DEG C of perseverances
Temperature calcining 18h, is finally cooled to room temperature, and deionized water is fully washed, the rich lithium tertiary cathode of drying to obtain fluorination treatment
Material LiNi1/3Co1/3Mn1/3O1.9F0.1。
To obtained rich lithium tertiary cathode material LiNi1/3Co1/3Mn1/3O1.9F0.1, using X-ray diffractometer and scanning
Electronic Speculum is characterized to the nickel-cobalt lithium manganate cathode material, and the XRD spectrum of products therefrom is as shown in figure 1, ESEM such as Fig. 2 institutes
Show.
With rich lithium tertiary cathode material LiNi1/3Co1/3Mn1/3O1.9F0.1Prepare full battery：
It is in proportion 96%:1.8%:2.2% weighs respectively LiNi1/3Co1/3Mn1/3O1.9F0.1Positive electrode, SuperP leads
Electric carbon black and PVDF binding agents, with NMP as solvent, are coated on aluminium foil after being well mixed and make positive plate, and negative plate adopts graphite
For active material, its content is 95.5%, and conductive black is conductive agent, and content is 2%, CMC and SBR is binding agent, its total amount
For 2.5%, with Celgard 2300 as barrier film, the LiPF6/EC of 1mol/L:DMC (volume ratios 1:1) it is electrolyte, is assembled into
063048 box hat battery, its charging/discharging voltage scope is 3.0V～4.2V, and 0.5C first discharge specific capacities are 159.6mAh/g, such as
Capability retention is 99.5% after circulating 100 times shown in Fig. 3, as shown in Figure 4.
Embodiment 3：
A kind of preparation method of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped is present embodiments provided, methods described includes
Following steps：
(1) mixed aqueous solution (nickel ion, the manganese ion of the sulfate that 200mL ion concentrations are 2mol/L nickel, cobalt and manganese are taken
It is 17 with the mol ratio of cobalt ions:6:17), it is added in the reactor with agitating device, leads to argon gas, while being slowly added to dense
Spend for 5mol/L sodium hydroxide solution and concentration be 5mol/L ammonia spirits, under an inert atmosphere in 65 DEG C react 18h, adjust
PH is stable 13, Jing filtering with after supersound washing, obtains Ni0.425Co0.15Mn0.425(OH)2Precursor pulp；
(2) Ni for obtaining step (1)1/3Co1/3Mn1/3(OH)2Precursor pulp is heat-treated 5h at 550 DEG C, then presses
LiNi0.425Co0.15Mn0.425O1.8F0.2Stoichiometric proportion weigh lithium hydroxide and lithium fluoride (mol ratio be 4:1) mix, then to
Wherein (mol ratio is 1 to the mixture of the lithium chloride and potassium chloride of 5 times of addition nickel cobalt manganese composite precursor and lithium source gross mass:9),
Mechanically it is well mixed, and base substrate is prepared by cake-making machine；
(3) base substrate obtained by step (2) is placed in air atmosphere stove, with the ramp of 10 DEG C/min, at 1000 DEG C
Calcining at constant temperature 12h, is finally cooled to room temperature, and deionized water is fully washed, and the rich lithium ternary of drying to obtain fluorination treatment is just
Pole material LiNi0.425Co0.15Mn0.425O1.8F0.2。
With rich lithium tertiary cathode material LiNi0.425Co0.15Mn0.425O1.8F0.2Prepare full battery：
It is in proportion 96%:1.8%:2.2% weighs respectively LiNi0.425Co0.15Mn0.425O1.8F0.2Positive electrode, Super
P conductive blacks and PVDF binding agents, with NMP as solvent, are coated on aluminium foil after being well mixed and make positive plate, and negative plate adopts stone
Ink is active material, and its content is 95.5%, and conductive black is conductive agent, and content is 2%, CMC and SBR is binding agent, and its is total
Measure as 2.5%, with Celgard 2300 as barrier film, the LiPF6/EC of 1mol/L:DMC (volume ratios 1:1) it is electrolyte, is assembled into
063048 box hat battery, its charging/discharging voltage scope is 3.0V～4.2V, and 0.5C first discharge specific capacities are 161.4mAh/g, are followed
Capability retention is 94.5% after ring 100 times.
Embodiment 4：
Present embodiments provide a kind of preparation method of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped, methods described except
The ion concentration of mixed aqueous solution is 3mol/L in step (1), and the mol ratio of nickel ion, cobalt ions and manganese ion is 6:2:3, alkali
Liquid concentration is 2mol/L, and ammonia concn is 6mol/L, adjusts pH stable 14；Heat treatment temperature is 530 DEG C in step (2), is helped
The consumption of flux is the flux of 1 times of nickel cobalt manganese composite precursor and lithium source gross mass；Calcining heat is described in step (3)
700 DEG C, calcination time is that unclassified stores consumption is in the same manner as in Example 1 with preparation method outside 10h, and richness lithium ternary is being obtained just
Pole material LiNi0.5Co0.2Mn0.3O1.85F0.15。
With rich lithium tertiary cathode material LiNi0.5Co0.2Mn0.3O1.85F0.15Full battery is prepared, in preparation process and embodiment 1
Identical, its charging/discharging voltage scope is 3.0V～4.2V, and 0.5C first discharge specific capacities are 158.6mAh/g, after circulating 100 times
Capability retention is 93.7%.
Comparative example 1：
This comparative example provide a kind of Fluorin doped nickel cobalt manganese systems tertiary cathode material preparation method, methods described except
Do not carry out Fluorin doped (being added without Fluorine source in step (2)) outward, unclassified stores consumption and preparation method with phase in embodiment 1
Together, the tertiary cathode material LiNi of the fluorine that undopes is obtained0.5Co0.2Mn0.3O2
With the tertiary cathode material LiNi0.5Co0.2Mn0.3O1.85Prepare full battery, preparation process and phase in embodiment 1
Together, its charging/discharging voltage scope is 3.0V～4.2V, and 0.5C first discharge specific capacities are 154.6mAh/g, are held after circulating 100 times
Amount conservation rate is 92.2%.
Comparative example 2：
This comparative example provides a kind of preparation method of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped, the preparation method
In addition to step (2) is not heat-treated, unclassified stores consumption is in the same manner as in Example 1 with preparation method, and prepared ternary is just
Pole material LiNi0.5Co0.2Mn0.3O1.85F0.15。
With the tertiary cathode material LiNi0.5Co0.2Mn0.3O1.85F0.15Full battery is prepared, in preparation process and embodiment 1
Identical, its charging/discharging voltage scope is 3.0V～4.2V, and 0.5C first discharge specific capacities are 160.9mAh/g, after circulating 100 times
Capability retention is 91.8%.
Comparative example 3：
This comparative example provides a kind of preparation method of the nickel cobalt manganese systems tertiary cathode material of Fluorin doped, the preparation method
Except step (2) is：To the Ni that step (1) is obtained0.5Co0.2Mn0.3(OH)2Press in precursor pulp
LiNi0.5Co0.2Mn0.3O1.85F0.15Stoichiometric proportion weigh lithium hydroxide and lithium fluoride (mol ratio be 25:3) mix, then to
The equimolar potassium chloride and sodium chloride of 10 times of gross mass are wherein added, then 6h is heat-treated at 500 DEG C, is cooled down, ball milling is mixed
Close uniform, and prepared outside base substrate by cake-making machine, unclassified stores consumption is in the same manner as in Example 1 with preparation method, be obtained three
First positive electrode LiNi0.5Co0.2Mn0.3O1.85F0.15。
With the tertiary cathode material LiNi0.5Co0.2Mn0.3O1.85F0.15Full battery is prepared, in preparation process and embodiment 1
Identical, its charging/discharging voltage scope is 3.0V～4.2V, and 0.5C first discharge specific capacities are 159.2mAh/g, after circulating 100 times
Capability retention is 89.4%.
The result of integrated embodiment 1-4 and comparative example 1-3 can be seen that the present invention with fuse salt as reaction medium, can protect
Card reactant has larger diffusion rate, and so as to ensure nucleation homogeneity, and then it is good to be eventually exhibited as the uniformity of material；Together
When, by reaction medium of fuse salt the homogeneity of product of different batches can also be made to be guaranteed.
The fluorine adulterated in the present invention has highest electronegativity and very high free energy, by fused salt fluorination treatment technology,
The energy density and cyclical stability of material are favorably improved, and then are made with the charge and discharge of battery obtained in material prepared by the present invention
Piezoelectric voltage scope is 3.0V～4.2V, and 0.5C first discharge specific capacities can be more than 160mAh/g, and capacity keeps after circulating 100 times
Rate reaches as high as 99%；
The average grain diameter of the nickel cobalt manganese systems tertiary cathode material of obtained Fluorin doped of the invention is uniform, and cycle performance is excellent,
Preparation method process is simple, low production cost, efficient energy-saving is suitable for industrialized production.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff it will be clearly understood that any improvement in the present invention, the equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (9)
1. the preparation method of the nickel cobalt manganese systems tertiary cathode material of a kind of Fluorin doped, it is characterised in that methods described includes following
Step：
(1) by the aqueous solution of transition metal source, alkali lye and ammoniacal liquor mix, stir and heat and reacted, reaction gained precipitate into
It is aged, be filtered, washed and dried after, obtain nickel cobalt manganese composite precursor；
(2) step (1) gained nickel cobalt manganese composite precursor is heat-treated at 500 DEG C～550 DEG C, then with lithium source and fluorine
Source mixes, and adds flux, mixes and make base substrate；
(3) step (2) base substrate is placed in in reacting furnace the calcining at constant temperature at 700 DEG C～1000 DEG C, then Jing coolings, washing
And drying, obtain the nickel cobalt manganese systems tertiary cathode material of Fluorin doped.
2. preparation method according to claim 1, it is characterised in that mistake in step (1) the transition metal saline solution
Source metal is crossed for nickel source, cobalt source and manganese source；
Preferably, the nickel source be nickel sulfate, nickelous carbonate, nickel nitrate or nickel hydroxide in any one or at least two group
Close；
Preferably, the cobalt salt be cobaltous sulfate, cobalt carbonate, cobalt nitrate or cobalt hydroxide in any one or at least two group
Close；
Preferably, the manganese salt be manganese sulfate, manganese carbonate, manganese nitrate or manganous hydroxide in any one or at least two group
Close.
3. preparation method according to claim 1 and 2, it is characterised in that in step (1) the transition metal saline solution
The mol ratio of nickel ion, cobalt ions and manganese ion is (1～8):(1～2):(1～3), preferably (1～6):(1～2):(1～
3)；
Preferably, the total ion concentration of nickel ion, cobalt ions and manganese ion is in step (1) the transition metal saline solution
2mol/L～3mol/L, preferably 2mol/L.
4. the preparation method according to any one of claim 1-3, it is characterised in that alkali lye described in step (1) is hydrogen-oxygen
Change in sodium, potassium hydroxide, ammonium carbonate or sodium carbonate any one or at least two aqueous solution；
Preferably, the concentration of step (1) alkali lye is 2mol/L～10mol/L, preferably 2mol/L～5mol/L；
Preferably, the concentration of step (1) ammoniacal liquor is 3mol/L～6mol/L, preferably 5mol/L.
5. the preparation method according to any one of claim 1-4, it is characterised in that step (1) stirring is stirred for machinery
Mix, preferably ultrasonic agitation；
Preferably, step (1) heating-up temperature is 50 DEG C～65 DEG C, preferably 55 DEG C；
Preferably, the pH that reaction system is controlled in step (1) course of reaction is 10～14, preferably 11～12；
Preferably, the reaction time of step (1) reaction is 18h～24h；
Preferably, the reaction atmosphere of step (1) reaction is inert atmosphere；
Preferably, the inert atmosphere be helium atmosphere, argon gas atmosphere or neon atmosphere in any one or at least two group
Close.
6. the preparation method according to any one of claim 1-5, it is characterised in that the time of step (2) heat treatment
For 5h～7h；
Preferably, step (2) lithium source be lithium hydroxide, lithium carbonate, lithium nitrate or lithium acetate in any one or at least two
The combination planted；
Preferably, the consumption of step (2) lithium source and the ratio of the mole of presoma are (1.0～1.08):1；
Preferably, step (2) Fluorine source be lithium fluoride, potassium fluoride or ammonium fluoride in any one or at least two combination；
Preferably, the consumption of step (2) Fluorine source and the ratio of the mole of presoma are (0.05～0.2):1；
Preferably, step (2) flux be the chloride of lithium, in the chloride of sodium or the chloride of potassium any one or extremely
Few two kinds combination；
Preferably, the consumption of step (2) flux is 1 times～10 times of nickel cobalt manganese composite precursor and lithium source gross mass；
Preferably, step (2) is described is mixed into mechanical mixture；
Preferably, the mechanical mixture be grind, stir or ball milling in any one or at least two combination.
7. the preparation method according to any one of claim 1-6, it is characterised in that reacting furnace described in step (3) is sky
Gas atmosphere furnace；
Preferably, the heating rate in step (3) reacting furnace is 2 DEG C/min～10 DEG C/min；
Preferably, the temperature of step (3) calcining at constant temperature is 800 DEG C～900 DEG C；
Preferably, the time of step (3) calcining at constant temperature is 10h～18h, preferably 15h～16h；
Preferably, step (3) is described is cooled to be cooled to 25 DEG C～30 DEG C；
Preferably, step (3) washing is to be washed with deionized.
8. the preparation method according to any one of claim 1-7, it is characterised in that the method comprising the steps of：
(1) it is (1～6) by the mol ratio of nickel ion, cobalt ions and manganese ion:(1～2):The total ion concentration of (1～3) is
The nickel source of 2mol/L, the aqueous solution of cobalt source and manganese source, concentration are the ammonia of alkali lye and concentration for 5mol/L of 2mol/L～5mol/L
Water mixes, and being stirred and heated to 55 DEG C carries out under an inert atmosphere reaction 18h～24h, and reaction system is controlled in course of reaction
PH be 11～12, reaction gained precipitate into it is aged, be filtered, washed and dried after, obtain nickel cobalt manganese composite precursor；
(2) step (1) gained nickel cobalt manganese composite precursor is carried out into heat treatment 5h～7h at 500 DEG C～550 DEG C, then with lithium
Source and Fluorine source mix, and the consumption of lithium source is (1.0～1.08) with the ratio of the mole of presoma:1, the consumption and presoma of Fluorine source
Mole ratio be (0.05～0.2):1, add 1 times～10 times of nickel cobalt manganese composite precursor and lithium source gross mass and help
Flux, mixes and makes base substrate；
(3) step (2) base substrate is placed in reacting furnace with the ramp of 2 DEG C/min～10 DEG C/min, in 800 DEG C～
Calcining at constant temperature 15h～16h at 900 DEG C, then Jing coolings, washing and drying, obtain the nickel cobalt manganese systems tertiary cathode material of Fluorin doped
Material.
9. the nickel cobalt manganese systems tertiary cathode material of the Fluorin doped that the preparation method according to any one of claim 1-8 is prepared
Material, it is characterised in that the nickel cobalt manganese systems tertiary cathode material of the Fluorin doped is Li1+xNiαCoβMnγFyO2-y, wherein 0≤x≤
0.2,0<Y≤0.1,0<α<1,0<β<1,0<γ<1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683645A (en) * | 2011-03-17 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery |
| CN102738453A (en) * | 2012-07-11 | 2012-10-17 | 中国第一汽车股份有限公司 | High-tap-density lithium-enriched material prepared by using hydroxyl coprecipitation-fused salt method |
| CN103094523A (en) * | 2013-01-17 | 2013-05-08 | 东莞新能源科技有限公司 | Anode material for lithium ion battery and preparation method of anode material |
| CN104752700A (en) * | 2013-12-30 | 2015-07-01 | 三星精密化学株式会社 | Cathode active material for lithium secondary battery, method of fabricating the same, and lithium secondary battery including the same |
| CN105958053A (en) * | 2016-06-04 | 2016-09-21 | 苏州思创源博电子科技有限公司 | Preparation method for lithium ion battery from ternary positive electrode material |
-
2016
- 2016-12-21 CN CN201611190763.2A patent/CN106602015A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102683645A (en) * | 2011-03-17 | 2012-09-19 | 中国科学院宁波材料技术与工程研究所 | Preparation method of layered lithium-rich manganese base oxide of positive material of lithium ion battery |
| CN102738453A (en) * | 2012-07-11 | 2012-10-17 | 中国第一汽车股份有限公司 | High-tap-density lithium-enriched material prepared by using hydroxyl coprecipitation-fused salt method |
| CN103094523A (en) * | 2013-01-17 | 2013-05-08 | 东莞新能源科技有限公司 | Anode material for lithium ion battery and preparation method of anode material |
| CN104752700A (en) * | 2013-12-30 | 2015-07-01 | 三星精密化学株式会社 | Cathode active material for lithium secondary battery, method of fabricating the same, and lithium secondary battery including the same |
| CN105958053A (en) * | 2016-06-04 | 2016-09-21 | 苏州思创源博电子科技有限公司 | Preparation method for lithium ion battery from ternary positive electrode material |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108511710B (en) * | 2018-03-22 | 2020-09-11 | 中南大学 | Lithium-rich manganese-based lithium ion battery positive electrode material and preparation method thereof |
| CN108511710A (en) * | 2018-03-22 | 2018-09-07 | 中南大学 | Lithium-rich manganese-based anode material for lithium-ion batteries and preparation method thereof |
| CN108987742A (en) * | 2018-07-23 | 2018-12-11 | 内蒙古华夏新材料科技有限公司 | A kind of nickelic positive electrode of lithium ion battery and preparation method thereof |
| CN109546145A (en) * | 2018-11-29 | 2019-03-29 | 深圳清华大学研究院 | Anode material of lithium battery, preparation method, lithium battery anode and lithium battery |
| CN109638251A (en) * | 2018-12-12 | 2019-04-16 | 无锡晶石新型能源股份有限公司 | A kind of preparation method of the modified nickelic positive electrode of gradient sintering gas phase Fluorin doped |
| CN109713277A (en) * | 2018-12-29 | 2019-05-03 | 蜂巢能源科技有限公司 | Anode material for lithium-ion batteries and preparation method, lithium ion battery |
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