CN103606667A - Preparation method for manganese solid solution anode material of lithium ion battery material - Google Patents
Preparation method for manganese solid solution anode material of lithium ion battery material Download PDFInfo
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- CN103606667A CN103606667A CN201310609063.2A CN201310609063A CN103606667A CN 103606667 A CN103606667 A CN 103606667A CN 201310609063 A CN201310609063 A CN 201310609063A CN 103606667 A CN103606667 A CN 103606667A
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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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
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- 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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Abstract
The invention relates to a preparation method for a manganese solid solution anode material of a lithium ion battery material. The method is characterized in that nickel, manganese and aluminum ion mixed liquid is reacted with a precipitator under a nitrogen atmosphere, reaction products are aged, washed and dried to obtain a nickel-manganese-aluminum hydrogenate precursor, and the synthesized precursor has spherical shape, ideal granularity distribution and high compacting density. The precursor is mixed with a lithium-source compound and a doping compound, the mixture is secondarily sintered, and the manganese solid solution anode material is obtained. The synthesis process is simple, the process is easy to control, the energy consumption is low, the efficiency is high, the cost is low, and the industrialized production can be realized. The prepared precursor is in spherical shape, the particles are uniformly distributed, the compacting density is high, the discharging capacity of the battery is improved by doping the metal, and the cycling performance of the battery is stable.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries field, be specifically related to the preparation method that a kind of lithium ion battery material manganese is solid solution cathode material.
Technical background
At present, research is a lot of as the system of anode material for lithium-ion batteries, but real heavy industrialization also only has cobalt acid lithium (LiCoO
2).LiMn
2o
4compared with LiCoO
2raw material is relatively cheap, material thermal stability is slightly high, but the capacity of LiMn2O4 is lower.LiFePO
4synthesis material aboundresources, cost is low, environmentally friendly, and capacity is high, good cycle, but its volume energy density is lower.LiNiO
2because it synthesizes difficulty and compares LiCoO
2worsely overcharge safety problem and limited its application.Novel ternary compound oxides LiNi
1/3co
1/3mn
1/3o
2with LiCoO
2have identical structure, it has LiCoO
2advantage (stable circulation performance and high-energy-density), and low-cost, security performance outstanding, but at the bottom of its platform voltage, compacted density is also lower.The theoretical capacity of these positive electrodes is all below 200mAh/g above, make 3G electronic product that battery capacity is had relatively high expectations and the marketing development of electric automobile run into certain difficulty, therefore need to explore the novel anode material that theoretical capacity surpasses 200mAh/g, or use and can to lithium current potential, bring up to the high voltage type positive electrode of 5V left and right by what only have at present 4V left and right, to increasing the energy density of battery.
Wherein, can realize the specific capacity over 250mAh/g, and belong to the manganese based solid solution class (Li of 5V class positive electrode
2mnO
3-LiMO
2) be that positive electrode is paid close attention to by researcher very, be sent to great expectations.This material manufacturing cost and Li
2mnO
4approach, but have than the electrochemistry capacitance of the latter Geng Gao and more stable cycle performance, and high temperature and high rate capability superior, therefore there is larger researching value.The strong competitor of anode material for lithium-ion batteries of future generation.
At present, lithium ion manganese is solid solution cathode material xLi
2mnO
3-(1-x) LiMO
2synthetic method more, mainly contain high temperature solid-state method, sol-gal process, coprecipitation, spray pyrolysis, hydro thermal method, spray drying process etc.Product prepared by colloidal sol---gel method has the advantages such as chemical composition is even, purity is high, particle is little, stoichiometric proportion can accurately be controlled, but complex process, cost are higher, and pattern and the particle diameter of product are wayward.By spray pyrolysis, can within a short period of time, obtain pure-phase superfine powder under lower calcination temperature and better simply process conditions.Product has good chemical property, but only limits at present experimental study, fails to realize industrialization.Spray drying process is had relatively high expectations to production equipment, is not suitable for suitability for industrialized production.Although this method of hydro thermal method can obtain having spherical morphology, the good ternary material of chemical property, must have certain production scale just both economical in course of industrialization.
The Christopher of U.S. good fortune Flo-Rida-Low university adopts coprecipitation to prepare Li[Ni
xli
(1-2x)/3mn
(2-x)/3] O
2positive electrode.By transition metal nitrate (Ni (NO
3)
26H
2o and Mn (NO
3)
24H
2o) be dissolved in 50mL deionized water, then in 2h, splash into 400mLLiOHH
2in O.Excessive LiOH H
2o is in order to ensure transition metal (NixMn
2/3-x/3) (OH
2) precipitation completely.After the transition metal hydroxide that co-precipitation obtains filters in vacuum filter, deionized water washing is three times, after in drying box 180 ℃ of baking 10h.Dried precursor and LiOHH
2o mixes by stoichiometric proportion, and mixture grinds after 30min 480 ℃ of insulation 12h in migration reacting furnace, is incubated 12h after being warmed up to 900～1000 ℃ after pre-burning product compressing tablet in reacting furnace in air atmosphere, to quench and the cold two kinds of modes of stove are lowered the temperature.Research shows that, when x=1/5, the discharge capacity of material reaches 250mAh/g.(J?Electrochem?Soc,2010,157(11):A1202～A1211)
Recent year researcher to manganese be solid solution cathode material also in the middle of constantly exploring ，Wang Sui army etc. adopted coprecipitation and the synthetic solid solution cathode material Li[Ni of solid phase method
xli
(1-2x)/3mn
(2-x)/3] O
2(x=1/5,1/4,1/3).Adopt NiSO
4, MnSO
4react in the aqueous solution with LiOH, regulate pH value and reaction temperature, be eutectoid out M (OH)
2(M=Mn, Ni) precursor precipitation, then by the precursor and the LiOHH that generate
2o mixes, and at high temperature calcining generates lithium-rich anode material, and electro-chemical test shows under 40mA/g, 2.0～4.8V discharging condition, and electrode material first discharge capacity is 220mAh/g, is finally stabilized in 200mAh/g left and right.(Chem?J?Chinese?U,2010,30(12):2358～2362)
The domestic patent report about lithium-rich anode is less, in the patent of Jiangxi Jiangte Li-poly Material Co., Ltd. and Institutes Of Technology Of Jiangxi's co-applications (publication No. CN101694876), reported by co-precipitation and the synthetic lithium-rich manganese-based anode material of solid phase method, at 2.5～4.6V, 0.1C discharges and recharges under condition, specific discharge capacity is 250mAh/g, and it is 225mAh/g that 1C discharges and recharges specific discharge capacity under condition.
Publication number is that the patent documentation of CN101562245 discloses a kind of MnO of passing through
2the coated method that rich lithium solid solution cathode material is carried out to modification, the method can improve the high rate performance of rich lithium solid solution, electro-chemical test shows, the positive electrode discharge capacity when 2C discharge after coated reaches 245mAh/g, 50 this still can keep higher capacity after circulating.
Beijing University of Technology has announced a kind of synthetic method of spherical gradient lithium-rich anode material by patent CN102013481, synthetic material has the concentration gradient of certain Mn, improved the tap density of lithium-rich anode material, there is good comprehensive electrochemical, but preparation technology is more complicated, be not suitable for suitability for industrialized production.Li[Ni
xli
(1-2x)/3mn
(2-x)/3] O
2solid solution cathode material has the outstanding performances such as electrochemistry capacitance, but the irreversible capacity first that it is larger and poor high rate performance and part material occur that in cyclic process these unfavorable factors of phase transformation have suppressed its business-like development, therefore need to be prepared and exploration and the improvement of method of modifying aspect it, make it really meet business-like requirement.
Summary of the invention
The object of the invention is to for lithium ion battery material manganese is the raising of electrical property and the control problem of physical property of solid solution cathode material, it is the preparation method of solid solution cathode material that a kind of lithium ion battery material manganese is provided, prepared presoma glomeration pattern, even particle distribution, prepared positive electrode has improved discharge capacity and cycle performance.For this reason, the present invention is by the following technical solutions:
A kind of lithium ion battery material manganese is the preparation method of solid solution cathode material, it is characterized in that: nickel manganese aluminium ion mixed liquor and precipitation reagent are carried out to precipitation reaction, through ageing, washing, suction filtration, drying process, obtain nickel manganese aluminium hydroxide presoma, by described presoma, Li source compound and alloy M compound three ball milling mixing in proportion, mixture is through twice calcining, making manganese is solid solution cathode material, and detailed process is as follows:
(1) nickel manganese aluminum complex hydroxide Ni
xal
ymnz (OH)
2the preparation of presoma, x+z+y=1 wherein,
A, preparation mol ratio are Ni:Mn:Al=(0.3～0.6): (0.6～1.0): the mixed solution of the soluble nickel salt of (0.01～0.06), aluminum soluble salt, soluble manganese salt, and in mixed solution, the total concentration of three metal ion species is 0.3-1.1mol/L; And, the NaOH solution that compound concentration is 1-11mol/L, the ammonia spirit of 0.1-1mol/L;
B, with constant flow pump, described mixed solution and ammonia spirit are joined respectively in the reaction vessel of nitrogen atmosphere of high-speed stirred, dripping described NaOH solution, to regulate the pH of reaction solution be 10-12, and control synthesis temperature is 45-55 ℃, ageing 6-24h; Wherein the mol ratio of manganese ion and ammoniacal liquor is 1:2～12;
C, the sediment that above-mentioned steps ageing is obtained fully wash, after suction filtration, in 100～110 ℃ of vacuum, dry 10-12h, obtains Ni
xal yMn
z(OH)
2presoma;
(2) sintering
By presoma, Li source compound and M compound in proportion ball milling mix fully, then sintering in two steps: the first step in air or oxygen atmosphere with the heating that heats up of the speed of 0.1-10 ℃/min, at 450-750 ℃ of calcining at constant temperature 5-25h, second step is warming up to 700-950 ℃ of insulation 5-20h with the speed of 0.1-10 ℃/min again in air or oxygen atmosphere, cool to room temperature with the furnace, the lithium ion battery material manganese that makes doped metal ion is solid solution cathode material, wherein, presoma, the mol ratio of Li source compound is (0.4-0.6): 1, the doping of M compound is the 0.1-1.5% of presoma and the two gross mass of Li source compound,
In the M compound of described doping, described M is a kind of in aluminium, chromium, titanium, zinc, cobalt, molybdenum, magnesium metallic element, a kind of in the hydroxide that described M compound is M, oxide, chloride, nitrate, fluoride.
Adopting on the basis of technique scheme, the present invention also can adopt following further technical scheme:
Described soluble nickel salt is a kind of in nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate; Described soluble manganese salt is a kind of in manganese nitrate, manganese chloride, manganese acetate, manganese sulfate; Described solubility cobalt salt is a kind of in cobalt nitrate, cobalt chloride, cobalt acetate, cobaltous sulfate; Described aluminum soluble salt is a kind of in aluminum nitrate, aluminium chloride, aluminum acetate, aluminum sulfate.
Described Li source compound is selected from a kind of in a hydronium(ion) oxidation lithium, lithium acetate, lithium carbonate, lithium nitrate, lithium fluoride.
Owing to adopting technical scheme of the present invention, it is solid solution cathode material that the present invention adopts coprecipitation to prepare lithium ion battery manganese, and it is the improvement in performance method of solid solution cathode material that a kind of manganese is provided.The present invention has following beneficial effect: synthesis technique is simple, process is easy to control, energy consumption is low, efficiency is high, applicable industrialization with low cost is produced, prepared presoma glomeration pattern, even particle distribution, higher tap density, has improved the discharge capacity of battery by doping metals, the stable cycle performance of battery, is applicable to large-scale industrialization and produces.
Accompanying drawing explanation
Fig. 1 is the XRD figure of embodiment 1 sample;
Fig. 2 is the charging and discharging curve of embodiment 1 sample 0.2C;
Fig. 3 is the cycle performance of embodiment 1 sample 0.2C.
Fig. 4 is the Electronic Speculum figure of embodiment 1 sample.
Embodiment
Embodiment 1:
(1) take manganese sulfate (MnSO4H2O), aluminum sulfate (Al (NO3) 3.9H2O), nickelous sulfate (NiSO46H2O) is raw material, according to mol ratio 0.65:0.02:0.33, be dissolved in the mixed solution that is made into 1mol/L in deionized water, with deionized water, NaOH and the 0.48mol/L ammoniacal liquor of crossing 2mol/L be made into mixed solution equally.The volume ratio of mixed solution and ammoniacal liquor is 1:4.
(2) with the just above-mentioned nickel manganese of constant flow pump aluminium ion mixed liquor and ammonia spirit mixed solution, join respectively in the reaction vessel of nitrogen atmosphere of high-speed stirred.Dripping NaOH solution, to regulate pH be 12, ageing 10h, and the pH that controls ageing process is 12, the precipitation that above-mentioned steps is obtained is fully washed, suction filtration, in 100～110 ℃ of vacuum, after dry 12h, obtains Ni
0.33al
0.02mn
0.65(OH)
2presoma.
(3) take Ni
0.33al
0.02mn
0.65(OH)
2presoma 90.63g, lithium carbonate 48.26g, add the cobaltous fluoride ball milling of 2.06g to mix, be placed in the Muffle furnace of oxygen atmosphere, in oxygen atmosphere stove, with the speed of 2 ℃/min, be warming up to 750 ℃ of insulation 15h again, with the speed of 2 ℃/min, be warming up to 850 ℃ of calcining at constant temperature 20h, cool to room temperature with the furnace, making lithium ion battery material manganese is solid solution cathode material, by Fig. 4 visible material, be evenly distributed, there is obvious spherical structure, there is higher tap density.
(4) by gained manganese, be that solid solution cathode material is dressed up simulated battery, negative pole is metal lithium sheet, and barrier film is celgard2400, and electrolyte is LiPF
6(EC:DEC:DMC=1:1:1), record 0.2C first discharge capacity be 201.1mAh/g, 50 times circulation volume conservation rate is 98%.Discharge capacity by Fig. 2,3 visible material is higher, and cycle performance is good.
Embodiment 2:
Take manganese sulfate (MnSO4H2O), aluminium chloride (AlCl36H2O), nickelous sulfate (NiSO46H2O) is raw material, according to mol ratio 0.63:0.02:0.35, the mixed aqueous solution that preparation total concentration is 1.3mol/L, compound concentration is the NaOH solution of 4mol/L, the ammonia spirit that compound concentration is 0.66mol/L.The volume ratio of mixed solution and ammoniacal liquor is 1:3.5.
With constant flow pump, above-mentioned nickel manganese aluminium ion mixed liquor and ammonia spirit are added to stirring reaction in reactor, dripping NaOH solution adjusting pH is 11.5, ageing 18h, and the pH that controls ageing process is 11.5, the precipitation that above-mentioned steps is obtained is fully washed, suction filtration, in 100～110 ℃ of vacuum, after dry 12h, obtain Ni
0.35al
0.02mn
0.63(OH)
2presoma.
Take Ni
0.35al
0.02mn
0.63(OH)
2presoma 90.5g, lithium carbonate 44.55g, add the chromium oxide ball milling of 2.02g to mix, be placed in the Muffle furnace of air atmosphere, in air atmosphere stove, the speed with 2 ℃/min is warming up to 600 ℃ of insulation 19h again, with the speed of 5 ℃/min, be warming up to 750 ℃ of calcining at constant temperature 14h and cool to room temperature with the furnace, making lithium ion battery material manganese is solid solution cathode material.
By gained manganese, be that solid solution cathode material is dressed up simulated battery, barrier film is celgard2400, and negative pole is metal lithium sheet, and electrolyte is LiPF
6(EC:DEC:DMC=1:1:1), record 0.2C first discharge capacity be 200.2mAh/g, 50 times circulation volume conservation rate is 96.2%, so the discharge capacity of material is higher, cycle performance is good.
Embodiment 3:
Take manganese chloride (MnCl2H2O), aluminium chloride (AlCl36H2O), nickel chloride (NiCl26H2O) is raw material, according to mol ratio 0.64:0.02:0.3, the mixed aqueous solution that preparation total concentration is 1.1mol/L, compound concentration is the NaOH solution of 6mol/L, the ammonia spirit that compound concentration is 0.24mol/L.The anti-volume ratio of mixed solution and ammoniacal liquor is 1:3.
With the just above-mentioned nickel manganese of constant flow pump aluminium ion mixed liquor and ammonia spirit, add stirring reaction in reactor, dripping NaOH solution adjusting pH is 11, ageing 18h, and the pH that controls ageing process is 11, the precipitation that above-mentioned steps is obtained is fully washed, suction filtration, in 100～110 ℃ of vacuum, after dry 12h, obtain Ni
0.34al
0.02mn
0.64(OH)
2presoma.
Take Ni
0.35al
0.02mn
0.63(OH)
2presoma 60g, lithium carbonate 32.17g, add 0.92g aluminium oxide ball milling to mix, be placed in the Muffle furnace of oxygen atmosphere, in oxygen atmosphere stove, the speed with 5 ℃/min is warming up to 550 ℃ of insulation 20h again, speed with 2 ℃/min is warming up to 900 ℃ of calcining at constant temperature 25h, cool to room temperature with the furnace, making lithium ion battery material manganese is solid solution cathode material.
By gained manganese, be that solid solution cathode material is dressed up simulated battery, barrier film is celgard2400, and negative pole is metal lithium sheet, and electrolyte is LiPF
6(EC:DEC:DMC=1:1:1), record 0.2C first discharge capacity be 198.3mAh/g, 50 times circulation volume conservation rate is 98.2%, so the discharge capacity of material is higher, cycle performance is good.
Embodiment 4:
Ni:Al:Mn=0.33:0.03:0.0.64 in molar ratio, nickel acetate, aluminum acetate, manganese acetate mixed aqueous solution that preparation total concentration is 1.2mol/L, the NaOH solution that compound concentration is 2mol/L, the ammonia spirit that compound concentration is 0.4mol/L.The volume ratio of mixed solution and ammoniacal liquor is 1:2.5.
With constant flow pump, above-mentioned nickel manganese aluminium ion mixed liquor and ammonia spirit are added to stirring reaction in reactor, dripping NaOH solution adjusting pH is 12, ageing 20h, and the pH that controls ageing process is 12, the precipitation that above-mentioned steps is obtained is fully washed, suction filtration, in 100～110 ℃ of vacuum, after dry 12h, obtain Ni
0.33al
0.03mn
0.64(OH)
2presoma.
Take Ni
0.35al
0.02mn
0.63(OH)
2presoma 30g, lithium carbonate 14.85g, add the aluminum fluoride ball milling of 0.45g to mix, be placed in oxygen atmosphere stove and with the speed of 3 ℃/min, be warming up to 650 ℃ of insulation 16h again, in the speed with 5 ℃/min, be warming up to 850 ℃ of calcining at constant temperature 20h, cool to room temperature with the furnace, making lithium ion battery material manganese is solid solution cathode material.
By gained manganese, be that solid solution cathode material is dressed up simulated battery, barrier film is celgard2400, and negative pole is metal lithium sheet, and electrolyte is LiPF
6(EC:DEC:DMC=1:1:1), record 0.2C first discharge capacity be 199.6mAh/g, 60 times circulation volume conservation rate is 98.6%, so the discharge capacity of material is higher, cycle performance is good.
Embodiment 5:
Ni:Al:Mn=0.34:0.03:0.63 in molar ratio, nickel nitrate, aluminum nitrate, manganese nitrate mixed aqueous solution that preparation total concentration is 0.98mol/L, the NaOH solution that compound concentration is 3mol/L, the ammonia spirit that compound concentration is 0.48mol/L.The volume ratio of mixed solution and ammoniacal liquor is 1:2.5.
With constant flow pump, above-mentioned nickel manganese aluminium ion mixed liquor and ammonia spirit are added to stirring reaction in reactor, dripping NaOH solution adjusting pH is 12, ageing 18h, and the pH that controls ageing process is 12, the precipitation that above-mentioned steps is obtained is fully washed, suction filtration, in 100～110 ℃ of vacuum, after dry 12h, obtain Ni
0.34al
0.03mn
0.63(OH)
2presoma.
Take Ni
0.35al
0.02mn
0.63(OH)
2presoma 180.22g, lithium carbonate 92.01g, add the cobalt oxide ball milling of 2.99g to mix, be placed in the Muffle furnace of air atmosphere, in air atmosphere stove, the speed with 2 ℃/min is warming up to 500 ℃ of insulation 12h again, speed with 2 ℃/min is warming up to 850 ℃ of calcining at constant temperature 22h, cools to room temperature with the furnace, and making lithium ion battery material manganese is solid solution cathode material.
By gained manganese, be that solid solution cathode material is dressed up simulated battery, barrier film is celgard2400, and negative pole is metal lithium sheet, and electrolyte is LiPF
6(EC:DEC:DMC=1:1:1), record 0.2C first discharge capacity be 197.2mAh/g, 50 times circulation volume conservation rate is 98.7%, so the discharge capacity of material is higher, cycle performance is good.
Claims (3)
1. the preparation method that lithium ion battery material manganese is solid solution cathode material, it is characterized in that: nickel manganese aluminium ion mixed liquor and precipitation reagent are carried out to precipitation reaction, through ageing, washing, suction filtration, drying process, obtain nickel manganese aluminium hydroxide presoma, by described presoma, Li source compound and alloy M compound three ball milling mixing in proportion, mixture is through twice calcining, making manganese is solid solution cathode material, and detailed process is as follows:
(1) nickel manganese aluminum complex hydroxide Ni
xal
ymnz (OH)
2the preparation of presoma, x+z+y=1 wherein,
A, preparation mol ratio are Ni:Mn:Al=(0.3 ~ 0.6): (0.6 ~ 1.0): the mixed solution of the soluble nickel salt of (0.01 ~ 0.06), aluminum soluble salt, soluble manganese salt, and in mixed solution, the total concentration of three metal ion species is 0.3-1.1 mol/L; And compound concentration is the NaOH solution of 1-11 mol/L, the ammonia spirit of 0.1-1mol/L;
B, with constant flow pump, described mixed solution and ammonia spirit are joined respectively in the reaction vessel of nitrogen atmosphere of high-speed stirred, dripping described NaOH solution, to regulate the pH of reaction solution be 10-12, and control synthesis temperature is 45-55 ℃, ageing 6-24h; Wherein the mol ratio of manganese ion and ammoniacal liquor is 1:2 ~ 12;
C, the sediment that above-mentioned steps ageing is obtained fully wash, after suction filtration, in 100 ~ 110 ℃ of vacuum, dry 10-12h, obtains Ni
xal yMn
z(OH)
2presoma;
(2) sintering
By presoma, Li source compound and M compound in proportion ball milling mix fully, then sintering in two steps: the first step in air or oxygen atmosphere with the heating that heats up of the speed of 0.1-10 ℃/min, at 450-750 ℃ of calcining at constant temperature 5-25h, second step is warming up to 700-950 ℃ of insulation 5-20h with the speed of 0.1-10 ℃/min again in air or oxygen atmosphere, cool to room temperature with the furnace, the lithium ion battery material manganese that makes doped metal ion is solid solution cathode material, wherein, presoma, the mol ratio of Li source compound is (0.4-0.6): 1, the doping of M compound is the 0.1-1.5% of presoma and the two gross mass of Li source compound,
In the M compound of described doping, described M is a kind of in aluminium, chromium, titanium, zinc, cobalt, molybdenum, magnesium metallic element, a kind of in the hydroxide that described M compound is M, oxide, chloride, nitrate, fluoride.
2. preparation method according to claim 1, is characterized in that: described soluble nickel salt is a kind of in nickel nitrate, nickel chloride, nickel acetate, nickelous sulfate; Described soluble manganese salt is a kind of in manganese nitrate, manganese chloride, manganese acetate, manganese sulfate; Described solubility cobalt salt is a kind of in cobalt nitrate, cobalt chloride, cobalt acetate, cobaltous sulfate; Described aluminum soluble salt is a kind of in aluminum nitrate, aluminium chloride, aluminum acetate, aluminum sulfate.
3. preparation method according to claim 1, is characterized in that: described Li source compound is selected from a kind of in a hydronium(ion) oxidation lithium, lithium acetate, lithium carbonate, lithium nitrate, lithium fluoride.
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| CN104393281A (en) * | 2014-12-03 | 2015-03-04 | 刘娜 | Preparation method of manganese, nickel and lithium cathode material |
| CN104681809A (en) * | 2015-02-12 | 2015-06-03 | 长沙矿冶研究院有限责任公司 | Method for modifying lithium-rich manganese-based cathode material |
| CN105810934A (en) * | 2016-05-09 | 2016-07-27 | 北京工业大学 | Method capable of improving stability of crystal domain structure of lithium-rich layered oxide material |
| CN107482204A (en) * | 2017-08-21 | 2017-12-15 | 中国科学院成都有机化学有限公司 | A kind of metal solid solution modifies nickelic tertiary cathode material and preparation method thereof |
| CN107785566A (en) * | 2016-08-29 | 2018-03-09 | 中国科学院成都有机化学有限公司 | A kind of long-life nickel cobalt lithium aluminate cathode material and preparation method thereof |
| CN107973349A (en) * | 2017-11-24 | 2018-05-01 | 贵州大龙汇成新材料有限公司 | A kind of nickel manganese binary presoma for mixing aluminium and preparation method thereof |
| CN109802132A (en) * | 2017-11-16 | 2019-05-24 | 中国科学院宁波材料技术与工程研究所 | Positive electrode and preparation method thereof with nanometer rivet arrangement |
| CN110534731A (en) * | 2019-09-11 | 2019-12-03 | 李旭意 | A kind of preparation method of gradient tertiary cathode material |
| CN113479944A (en) * | 2021-09-07 | 2021-10-08 | 中南大学 | Preparation method of modified high-nickel ternary cathode material |
| CN113851641A (en) * | 2021-09-17 | 2021-12-28 | 天津市捷威动力工业有限公司 | High-entropy solid solution cathode material and preparation method and application thereof |
| CN114455645A (en) * | 2022-01-11 | 2022-05-10 | 广州明美新能源股份有限公司 | Lithium nickel manganese aluminum oxide positive electrode material and preparation method thereof |
| CN114665086A (en) * | 2022-02-18 | 2022-06-24 | 中国科学院青海盐湖研究所 | Lithium-rich manganese-based positive electrode material and preparation method thereof |
| US11437617B2 (en) * | 2017-07-21 | 2022-09-06 | Industry-University Cooperation Foundation Hanyang University | Metal-doped cathode active material for sodium secondary battery, method for manufacturing the same, and sodium secondary battery comprising the same |
| CN115557544A (en) * | 2022-10-28 | 2023-01-03 | 安徽格派新能源有限公司 | Preparation method of high-capacity lithium nickel manganese oxide |
| CN117038956A (en) * | 2023-10-09 | 2023-11-10 | 浙江帕瓦新能源股份有限公司 | Cobalt-free high-nickel positive electrode material, preparation method thereof and lithium ion battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101694876A (en) * | 2009-10-22 | 2010-04-14 | 江西江特锂电池材料有限公司 | Lithium-rich manganese-based anode material and preparation method thereof |
| CN102306765A (en) * | 2011-08-18 | 2012-01-04 | 合肥国轩高科动力能源有限公司 | Preparation method for nickel-manganese-cobalt anode material of lithium ion battery |
| CN102315429A (en) * | 2011-08-04 | 2012-01-11 | 深圳市天骄科技开发有限公司 | Preparation method of aluminum-doped material of cathode of lithium ion battery with solid phase process |
| CN102394293A (en) * | 2011-10-17 | 2012-03-28 | 江苏科捷锂电池有限公司 | High-performance lithium ion battery anode material NCM and manufacturing method thereof |
| CN102569781A (en) * | 2012-03-27 | 2012-07-11 | 天津理工大学 | High-voltage lithium ion battery cathode material and preparation method thereof |
| CN102576866A (en) * | 2009-09-30 | 2012-07-11 | 索尔维公司 | Positive active electrode material for lithium secondary battery, process for preparing the same and lithium secondary battery |
| CN102569780A (en) * | 2012-02-28 | 2012-07-11 | 南京航空航天大学 | Method for preparing lithium ion battery cathode material with layered structure |
-
2013
- 2013-11-26 CN CN201310609063.2A patent/CN103606667A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102576866A (en) * | 2009-09-30 | 2012-07-11 | 索尔维公司 | Positive active electrode material for lithium secondary battery, process for preparing the same and lithium secondary battery |
| CN101694876A (en) * | 2009-10-22 | 2010-04-14 | 江西江特锂电池材料有限公司 | Lithium-rich manganese-based anode material and preparation method thereof |
| CN102315429A (en) * | 2011-08-04 | 2012-01-11 | 深圳市天骄科技开发有限公司 | Preparation method of aluminum-doped material of cathode of lithium ion battery with solid phase process |
| CN102306765A (en) * | 2011-08-18 | 2012-01-04 | 合肥国轩高科动力能源有限公司 | Preparation method for nickel-manganese-cobalt anode material of lithium ion battery |
| CN102394293A (en) * | 2011-10-17 | 2012-03-28 | 江苏科捷锂电池有限公司 | High-performance lithium ion battery anode material NCM and manufacturing method thereof |
| CN102569780A (en) * | 2012-02-28 | 2012-07-11 | 南京航空航天大学 | Method for preparing lithium ion battery cathode material with layered structure |
| CN102569781A (en) * | 2012-03-27 | 2012-07-11 | 天津理工大学 | High-voltage lithium ion battery cathode material and preparation method thereof |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393281B (en) * | 2014-12-03 | 2017-01-25 | 梁贺君 | Preparation method of manganese, nickel and lithium cathode material |
| CN104393281A (en) * | 2014-12-03 | 2015-03-04 | 刘娜 | Preparation method of manganese, nickel and lithium cathode material |
| CN104681809A (en) * | 2015-02-12 | 2015-06-03 | 长沙矿冶研究院有限责任公司 | Method for modifying lithium-rich manganese-based cathode material |
| CN104681809B (en) * | 2015-02-12 | 2017-11-17 | 长沙矿冶研究院有限责任公司 | The method of modifying of lithium-rich manganese-based anode material |
| CN105810934B (en) * | 2016-05-09 | 2019-07-05 | 北京工业大学 | A kind of stabilizing lithium rich layered oxide material crystalline domain structure method |
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| US11437617B2 (en) * | 2017-07-21 | 2022-09-06 | Industry-University Cooperation Foundation Hanyang University | Metal-doped cathode active material for sodium secondary battery, method for manufacturing the same, and sodium secondary battery comprising the same |
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| CN109802132A (en) * | 2017-11-16 | 2019-05-24 | 中国科学院宁波材料技术与工程研究所 | Positive electrode and preparation method thereof with nanometer rivet arrangement |
| CN107973349A (en) * | 2017-11-24 | 2018-05-01 | 贵州大龙汇成新材料有限公司 | A kind of nickel manganese binary presoma for mixing aluminium and preparation method thereof |
| CN110534731A (en) * | 2019-09-11 | 2019-12-03 | 李旭意 | A kind of preparation method of gradient tertiary cathode material |
| CN113479944A (en) * | 2021-09-07 | 2021-10-08 | 中南大学 | Preparation method of modified high-nickel ternary cathode material |
| CN113851641A (en) * | 2021-09-17 | 2021-12-28 | 天津市捷威动力工业有限公司 | High-entropy solid solution cathode material and preparation method and application thereof |
| CN114455645A (en) * | 2022-01-11 | 2022-05-10 | 广州明美新能源股份有限公司 | Lithium nickel manganese aluminum oxide positive electrode material and preparation method thereof |
| CN114455645B (en) * | 2022-01-11 | 2024-02-06 | 广州明美新能源股份有限公司 | Nickel-manganese lithium aluminate positive electrode material and preparation method thereof |
| CN114665086A (en) * | 2022-02-18 | 2022-06-24 | 中国科学院青海盐湖研究所 | Lithium-rich manganese-based positive electrode material and preparation method thereof |
| CN115557544A (en) * | 2022-10-28 | 2023-01-03 | 安徽格派新能源有限公司 | Preparation method of high-capacity lithium nickel manganese oxide |
| CN117038956A (en) * | 2023-10-09 | 2023-11-10 | 浙江帕瓦新能源股份有限公司 | Cobalt-free high-nickel positive electrode material, preparation method thereof and lithium ion battery |
| CN117038956B (en) * | 2023-10-09 | 2024-01-23 | 浙江帕瓦新能源股份有限公司 | Cobalt-free high-nickel positive electrode material, preparation method thereof and lithium ion battery |
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