CN101694876A - Lithium-rich manganese-based anode material and preparation method thereof - Google Patents

Lithium-rich manganese-based anode material and preparation method thereof Download PDF

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CN101694876A
CN101694876A CN200910186311A CN200910186311A CN101694876A CN 101694876 A CN101694876 A CN 101694876A CN 200910186311 A CN200910186311 A CN 200910186311A CN 200910186311 A CN200910186311 A CN 200910186311A CN 101694876 A CN101694876 A CN 101694876A
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lithium
manganese
salt
anode material
nickel
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钟盛文
胡伟
张骞
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Jiangxi Jiangte Lithium Lon Battery Material Co Ltd
Jiangxi University of Science and Technology
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Jiangxi Jiangte Lithium Lon Battery Material Co Ltd
Jiangxi University of Science and Technology
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Abstract

The invention relates to a lithium-ion secondary battery anode material technology, in particular to a lithium-rich manganese-based anode material Li(Li(1-2x)/3Nix-aMyMn(2-x)/3-b)O2 (M is Co, Al, Ti, Mg and Cu) and a preparation method thereof. A general formula of the lithium-rich manganese-based anode material is as follows: Li(Li(1-2x)/3Nix-aMyMn(2-x)/3-b)O2 (M is Co, Al, Ti, Mg and Cu), wherein x is more than 0 and less than or equal to 0.5, when M is Co and Al, y is more than 0 and less than 2x, a is equal to b, and b is equal to y/2; when M is Ti, y is more than 0 and less than (2-x)/3, a is equal to 0, and b is equal to y; and when M is Mg and Cu, y is more than 0 and less than x, a is equal to y, and b is equal to 0. The invention has high specific discharge capacity, excellent normal temperature and high temperature cycle performance, good safety, low raw material cost and production cost, and very high cost-performance ratio.

Description

Lithium-rich manganese-based anode material and preparation method thereof
Technical field
The present invention relates to the lithium ion secondary battery anode material technology, particularly lithium-rich manganese-based anode material Li[Li (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) and preparation method thereof.
Background technology
Anode material for lithium-ion batteries is the crucial raw material of lithium ion battery, the quality of its performance has determined the performance of lithium ion battery, the height of its price has determined the cost of lithium ion battery, positive electrode in the market is based on cobalt acid lithium, and materials such as spinel lithium manganate, nickle cobalt lithium manganate, lithium nickel cobalt dioxide, LiFePO 4 have also occupied certain market share.Cobalt acid lithium is to take the lead in realizing commercial positive electrode, its stable performance, simple, the technical maturity of preparation, but global cobalt resource is in short supply, and China is poor cobalt country, therefore the production cost of cobalt acid lithium is very high, and product price is high, and cobalt has certain toxicity, the development of cobalt acid lithium has been subjected to obstruction, needs other material as its substitute.Spinel lithium manganate is cheapest in the market positive electrode, fail safe, but its specific capacity is lower, high temperature cyclic performance is poor.Nickle cobalt lithium manganate is compared with cobalt acid lithium, and price is low, the specific capacity height, and fail safe is good, and is more friendly to environment, but its platform voltage is low, and compacted density is also lower.Lithium nickel cobalt dioxide has good chemical property, but its price than nickle cobalt lithium manganate height, and poor stability.
Compare lithium-rich manganese-based anode material Li[Li with positive electrode in the market (1-2x)/3Ni xMn (2-x)/3] O 2Because transition metal is based on manganese, the manganese aboundresources, cheap, and environmentally friendly, be a kind of new material therefore with better development prospect.Li[Li (1-2x)/3Ni xMn (2-x)/3] O 2Material is Li 2MnO 3With LiMn 0.5Ni 0.5O 2Solid solution, be a kind of composite construction, it has very high specific capacity under higher charging voltage, bibliographical information Li is arranged 1.2Ni 0.2Mn 0.6O 2Material is 288mAh/g at 2-4.8V with the initial discharge specific capacity that the electric current of 20mA/g discharges and recharges, but its cyclical stability is very poor, and 30 times circulation back specific discharge capacity just drops to 213mAh/g.The Li[Li that from present document, is reported (1-2x)/3Ni xMn (2-x)/3] O 2Material there is obvious defects, and the first, the Li[Li that reports in the document (1-2x)/3Ni xMn (2-x)/3] O 2The height ratio capacity of material all discharges and recharges under very low multiplying power and obtains, and when multiplying power increased, specific capacity descended very fast, and the high rate performance of material is relatively poor; The second, Li[Li (1-2x)/3Ni xMn (2-x)/3] O 2Material has only when it is charged to 4.5V just can obtain higher specific capacity when above, if the specific capacity that charging obtains under lower voltage is more much lower than materials such as the sour lithiums of cobalt.In sum, present Li[Li (1-2x)/3Ni xMn (2-x)/3] O 2Material property does not reach requirement of actual application, therefore presses for it is carried out improvement in performance, so that it possesses better performance, realizes suitability for industrialized production as early as possible.
Summary of the invention
The object of the invention provides a kind of height ratio capacity, high magnification, cheap, chemical property is good, structural stability reaches high security well lithium-rich manganese-based anode material Li[Li (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu).
Another object of the present invention is to provide described lithium-rich manganese-based anode material Li[Li (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2The preparation method of (M=Co, Al, Ti, Mg, Cu).
Technical solution of the present invention: lithium-rich manganese-based anode material, its general formula is:
Li[Li (1-2x)/3Ni x-aM yMn (2-x)/3-b]O 2(M＝Co、Al、Ti、Mg、Cu)，
0＜x≤0.5 wherein,
When M=Co, Al, 0＜y＜2x, a=b=y/2;
When M=Ti, 0＜y＜(2-x)/3, a=0, b=y;
When M=Mg, Cu, 0＜y＜x, a=y, b=0.
The microstructure of described lithium-rich manganese-based anode material is Li 2MnO 3And LiMO 2Layered composite structure.
The preparation method of described lithium-rich manganese-based anode material may further comprise the steps:
A) soluble nickel, manganese, M salt are pressed (x-a): [(2-x)/and 3-b]: the mol ratio of y is dissolved in the deionized water, is mixed with the solution that total concentration is 0.5～4mol/L, wherein, and 0＜x≤0.5, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0;
B) mixed solution of preparation aqueous slkali or alkali and ammoniacal liquor, alkali concn is 1～8mol/L, the ammoniacal liquor molar concentration is 0.1～4mol/L;
C) in reactor, add the deionized water that accounts for reactor total measurement (volume) 10%-30%, described nickel, manganese, M salting liquid are pumped in the reactor, mixed solution with described aqueous slkali or alkali and ammoniacal liquor is pumped in the reactor simultaneously, material in the reactor is stirred, temperature, pH value in the control reactor generate presoma [Ni by coprecipitation reaction (x-a)/(x+ (2-x)/3)M Y/ (x+ (2-x)/3)Mn ((2-x)/3-b)/(x+ (2-x)/3)] (OH) 2Precipitation;
D) presoma is filtered, washing, oven dry back and lithium compound be that { [1+ (1-2x)/3]/[x-a+y+ (2-x)/3-b]+z}: 1 ratio is evenly mixed by the ratio of the total molal quantity of the molal quantity of lithium and nickel, manganese, M, wherein, 0＜x≤0.5,0≤z≤0.1, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0;
E) homogeneous mixture of presoma and lithium compound is at high temperature fired, promptly obtained
Li[Li (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) material.
Soluble nickel salt described in the step (a) can be a kind of or its salt-mixture in nickelous sulfate, nickel nitrate, nickel chloride, the nickel acetate; Soluble manganese salt can be a kind of or its salt-mixture in manganese sulfate, manganese nitrate, manganese chloride, the manganese acetate; The solubility cobalt salt can be a kind of or its salt-mixture in cobaltous sulfate, cobalt nitrate, cobalt chloride, the cobalt acetate; Aluminum soluble salt can be a kind of or its salt-mixture in aluminum sulfate, aluminum nitrate, the aluminium chloride; The solubility titanium salt can be a titanium tetrachloride; The solubility magnesium salts can be a kind of or its salt-mixture in magnesium sulfate, magnesium chloride, magnesium nitrate, the magnesium acetate; Soluble copper salt can be a kind of or its salt-mixture in copper sulphate, copper chloride, copper nitrate, the copper acetate.
Alkali described in the step (b) can be a kind of in NaOH, potassium hydroxide, lithium hydroxide, the sodium carbonate, or the mixture of NaOH, potassium hydroxide, lithium hydroxide, and its concentration is 1-8mol/L.
Nickel described in the step (c), manganese, M solution are to join in the reactor with Sprayable on reactor top, and described aqueous slkali is to feed from the reactor bottom.
Temperature in the reactor described in the step (c) is 40～60 ℃, and the pH value is between 8～12.
Lithium compound described in the step (d) can be a kind of or its mixture in lithium hydroxide, lithium carbonate, the lithium nitrate, single ratio of planting lithium salts or mixing the total molal quantity of lithium molal quantity total in the lithium salts and nickel, manganese, M is { [1+ (1-2x)/3]/[x-a+y+ (2-x)/3-b]+z}: 1, wherein, 0＜x≤0.5,0≤z≤0.1, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0.
Filtration described in the step (d), washing are to make Na in the presoma +, K +Total content is less than 300ppm, and sulfate ion, chloride ion total content are less than 0.5%, and oven dry is to carry out between 80-150 ℃.
High-temperature firing described in the step (e) is that the heating rate with 1～20 ℃/min is warmed up to 400～800 ℃, insulation 2～20h, and then be warmed up to 800～1100 ℃, insulation 4～40h with the heating rate of 1～20 ℃/min.
Specifically, be that soluble nickel, manganese, M salt (as sulfate, chlorate, nitrate, acetate) are pressed (x-a): [(2-x)/and 3-b]: the mol ratio of y is dissolved in the deionized water, forming the transition metal ions total mol concentration is the homogeneous transparent solution of 0.5～4mol/L, wherein, 0＜x≤0.5, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0.The preparation molar concentration is the aqueous slkali of 1～8mol/L, perhaps prepares the mixed solution of alkali and ammoniacal liquor, and the ammoniacal liquor molar concentration is 0.1～4mol/L, and wherein alkali can be NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate etc.In reactor, add a certain amount of deionized water, be pumped into described nickel, manganese, M salting liquid and aqueous slkali (or mixed solution of alkali and ammoniacal liquor) in the reactor simultaneously, complete reaction forms mixed metal hydroxides or metal carbonate or metal base formula carbonate deposition, in the course of reaction material in the reactor is stirred, and the temperature in the control reactor at 40～60 ℃, pH value between 8～12, control the pH value by adjusting alkali lye flow velocity.With sedimentation and filtration, cleaning, dry, grind to form powdery, make presoma [Ni (x-a)/(x+ (2-x)/3)M Y/ (x+ (2-x)/3)Mn ((2-x)/3-b)/(x+ (2-x)/3)] (OH) 2With the presoma that makes and lithium compound in the ratio of the total molal quantity of the molal quantity of lithium and nickel, manganese, M for { [1+ (1-2x)/3]/[x-a+y+ (2-x)/3-b]+z}: 1 ratio is evenly mixed, wherein, 0＜x≤0.5,0≤z≤0.1, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0, lithium compound can be lithium carbonate, lithium hydroxide, lithium nitrate or its mixture.The homogeneous mixture of presoma and lithium compound is warmed up to 400～800 ℃ with the heating rate of 1～20 ℃/min, insulation 2～20h, and then being warmed up to 800～1100 ℃ with the heating rate of 1～20 ℃/min, insulation 4～40h obtains the described lithium-rich manganese-based anode material Li[Li of claim 1 (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu).
Advantage of the present invention:
The specific capacity height.With Li[Li of the present invention (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) material is the lithium ion cell charging cut-ff voltage height that positive electrode is made, and can reach 4.6V, and when discharging and recharging between 2.5～4.6V, specific discharge capacity can reach 250mAh/g.And also can obtain high specific discharge capacity under lower charging voltage, specific discharge capacity can reach 166mAh/g under the condition that discharges and recharges of 2.75-4.2V, 0.1C.
Stable cycle performance.With Li[Li of the present invention (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) material is that the lithium ion battery made of positive electrode is when discharging and recharging with 1C between 2.75-4.2V, the initial discharge specific capacity is 141mAh/g, 300 circulation back capability retentions are that 97%, 1600 circulation back capability retention is 74%; The multiplying power cycle performance is good, and the 6C specific discharge capacity is 94% of 0.5C;
High temperature circulation is stable and specific capacity is high.At 2.75-4.2V, 1C, when discharging and recharging under 55 ℃ the condition, the initial discharge specific capacity is 157mAh/g, 180 times circulation back capability retention is 92.2%.
Fail safe is good.With Li[Li of the present invention (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) material is that the lithium ion battery that positive electrode is made can pass through external short circuit, drift bolt experiment, and ability 5C10V overcharges, and Heat stability is good, environment maximum safety temperature are 170 ℃.
Environment-friendly material.Li[Li of the present invention (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) material cobalt content is few or do not contain cobalt, is a kind of environment amenable material.
Cost is low.Li[Li of the present invention (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) material is based on manganese, so cost is very low, and superiority of effectiveness clearly.
Li[Li provided by the invention (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) preparation methods is simple and easy, helps industrialized production.
Description of drawings
Fig. 1 Li[Li 0.067Ni 0.3Cu 0.1Mn 0.533] O 2The XRD figure of material.
Fig. 2 Li[Li 0.067Ni 0.3Co 0.2Mn 0.433] O 2The SEM figure of material.
Fig. 3 Li[Li 0.2Ni 0.19Al 0.02Mn 0.59] O 2The first charge-discharge curve of material (2.5～4.6V, 0.1C, room temperature).
Fig. 4 Li[Li 0.2Ni 0.19Al 0.02Mn 0.59] O 2The specific discharge capacity (2.75～4.2V, room temperature) of material under different multiplying.
Embodiment
Introduce content of the present invention by the following examples in detail, it is for the ease of understanding the present invention that embodiment is provided, and never is the invention of restriction this patent.
Lithium-rich manganese-based anode material molecular formula provided by the invention is Li[Li (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu), 0＜x≤0.5 wherein, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0.
Lithium-rich manganese-based material Li[Li provided by the present invention (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) uses as positive electrode in the lithium ion battery preparation.
Lithium-rich manganese-based anode material Li[Li provided by the present invention (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2The preparation method of (M=Co, Al, Ti, Mg, Cu) comprises following step:
A. soluble nickel, manganese, M salt are pressed (x-a): [(2-x)/and 3-b]: the mol ratio of y is dissolved in the deionized water, is mixed with the solution that total concentration is 0.5～4mol/L, wherein, and 0＜x≤0.5, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0;
B. prepare the mixed solution of aqueous slkali or alkali and ammoniacal liquor, alkali concn is 1～8mol/L, and the ammoniacal liquor molar concentration is 0.1～4mol/L;
C. in reactor, add a certain amount of deionized water, described nickel, manganese, M salting liquid are pumped in the reactor, simultaneously described aqueous slkali is pumped in the reactor, material in the reactor is stirred, temperature, pH value in the control reactor generate the presoma precipitation by coprecipitation reaction;
D. presoma is filtered, washing, oven dry back and lithium compound be that { [1+ (1-2x)/3]/[x-a+y+ (2-x)/3-b]+z}: 1 ratio is evenly mixed by the ratio of the total molal quantity of the molal quantity of lithium and nickel, manganese, M, wherein, 0＜x≤0.5,0≤z≤0.1, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0;
E. the homogeneous mixture with presoma and lithium compound carries out high temperature sintering, promptly obtains Li[Li (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2(M=Co, Al, Ti, Mg, Cu) material.
The described soluble nickel of step a, manganese, M salt can be sulfate, chlorate, nitrate, acetate or salt-mixture, the described alkali of step b can be NaOH, potassium hydroxide, lithium hydroxide, sodium carbonate etc., or the mixing in twos or the three of NaOH, potassium hydroxide, lithium hydroxide mix.The described lithium compound of step c can be lithium hydroxide, lithium carbonate, lithium nitrate or its mixture, and the temperature described in the step c between 8～12, is controlled pH value by regulating alkali lye (or mixed solution of alkali and ammoniacal liquor) flow velocity at 40～60 ℃, pH value.The described high temperature sintering of step e is that the homogeneous mixture of presoma and lithium compound is warmed up to 400-800 ℃ with the heating rate of 1～20 ℃/min, insulation 2-20h, and then be warmed up to 800～1100 ℃, insulation 4-40h with the heating rate of 1-20 ℃/min.
Embodiment 1
With nickel, manganese, aluminum metal ion molar percentage is 0.123: 0.850: 0.027, nickelous sulfate, manganese sulfate, aluminum sulfate are dissolved in the deionized water, being made into manganese, nickel, aluminium ion total concentration is the homogeneous transparent solution of 2mol/L, the sodium hydroxide solution of preparation 4mol/L is pumped into mixed salt solution and sodium hydroxide solution simultaneously and carries out coprecipitation reaction in the reactor.Precipitated product after filtration, cleaning, drying, obtain metal hydroxides presoma Mn 0.85Ni 0.123Al 0.027(OH) 2
Is that 1.77: 1 ratio is advanced evenly to mix with presoma and lithium carbonate in the ratio of the total molal quantity of the molal quantity of lithium and nickel, manganese, aluminium, with the powder pressing that evenly mixes, 450 ℃ of insulations 2 hours, be warmed up to 800 ℃ of insulations 40 hours then, obtain lithium-rich manganese-based material Li[Li 0.267Ni 0.09Al 0.02Mn 0.623] O 2
Li[Li with preparation 0.267Ni 0.09Al 0.02Mn 0.623] O 2For positive electrode is assembled into AA type battery.At 2.5-4.6V, 0.1C discharges and recharges under the condition, and specific discharge capacity is 250mAh/g.
Embodiment 2
With nickel, manganese, aluminum metal ion molar percentage is 0.238: 0738: 0.025., nickel chloride, manganese sulfate, aluminium chloride are dissolved in the deionized water, being made into manganese, nickel, aluminium ion total concentration is the homogeneous transparent solution of 2mol/L, the sodium hydroxide solution of preparation 4mol/L is pumped into mixed salt solution and sodium hydroxide solution simultaneously and carries out coprecipitation reaction in the reactor.Precipitated product after filtration, cleaning, drying, obtain metal hydroxides presoma Mn 0.738Ni 0.238Al 0.025(OH) 2
Is that 1.54: 1 ratio is advanced evenly to mix with presoma and lithium carbonate in the ratio of the total molal quantity of the molal quantity of lithium and nickel, manganese, aluminium, with the powder pressing that evenly mixes, 550 ℃ of insulations 4 hours, be warmed up to 900 ℃ of insulations 20 hours then, obtain lithium-rich manganese-based material Li[Li 0.2Ni 0.19Al 0.02Mn 0.59] O 2
With Li[Li 0.2Ni 0.19Al 0.02Mn 0.59] O 2For positive electrode is assembled into AA type battery.At 2.5-4.6V, 0.1C discharges and recharges under the condition, and specific discharge capacity is identical with material among the embodiment 1, is 250mAh/g also.Discharge and recharge at other voltage range and also to have shown higher capacity, 2.5-4.2V is when 0.3C discharges and recharges, specific discharge capacity is between the 150-160mAh/g, 2.5-4.3V when 0.3C discharged and recharged, specific discharge capacity was between the 160-170mAh/g, 2.5-4.4V, 0.3C when discharging and recharging, specific discharge capacity is between the 170-180mAh/g, 2.5-4.5V, 0.3C when discharging and recharging, specific discharge capacity is between the 180-190mAh/g.At 2.75-4.2V, carry out charge and discharge cycles under the condition of 1C, the initial discharge specific capacity is 141mAh/g, 300 circulation back capability retentions are that 97%, 1600 circulation back capability retention is 74%; The multiplying power cycle performance is good, and the 6C specific discharge capacity is 94% of 0.5C; High temperature circulation is stable and specific capacity is high, at 2.75-4.2V, and 1C, when discharging and recharging under 55 ℃ the condition, the initial discharge specific capacity is 157mAh/g, 180 times circulation back capability retention is 92.2%.
Embodiment 3
With nickel, manganese, copper metal ion molar percentage is 0.231: 0.654: 0.115, nickelous sulfate, manganese sulfate, copper sulphate are dissolved in the deionized water, being made into manganese, nickel, copper ion total concentration is the homogeneous transparent solution of 2mol/L, the potassium hydroxide solution of preparation 4mol/L is pumped into mixed salt solution and sodium hydroxide solution simultaneously and carries out coprecipitation reaction in the reactor.Precipitated product after filtration, cleaning, drying, obtain metal hydroxides presoma Mn 0.654Ni 0.231Cu 0.115(OH) 2
Is that 1.35: 1 ratio is advanced evenly to mix with presoma and lithium carbonate in the ratio of the total molal quantity of the molal quantity of lithium and nickel, manganese, copper, with the powder pressing that evenly mixes, 500 ℃ of insulations 15 hours, be warmed up to 1000 ℃ of insulations 8 hours then, obtain lithium-rich manganese-based material Li[Li 0.133Ni 0.2Cu 0.1Mn 0.567] O 2
With Li[Li 0.133Ni 0.2Cu 0.1Mn 0.567] O 2For positive electrode is assembled into the AA battery.At 2.5-4.6V, 1C discharges and recharges that specific discharge capacity is 225mAh/g under the condition.
Embodiment 4
With nickel, manganese, copper metal ion molar percentage is 0.322: 0.571: 0.107, nickelous sulfate, manganese sulfate, copper sulphate are dissolved in the deionized water, being made into manganese, nickel, copper ion total concentration is the homogeneous transparent solution of 2mol/L, the sodium carbonate liquor of preparation 2mol/L is pumped into mixed salt solution and sodium carbonate liquor simultaneously and carries out coprecipitation reaction in the reactor.Precipitated product after filtration, cleaning, drying, obtain carbonate precursor Mn 0.571Ni 0.322Cu 0.107CO 3
Is that 1.18: 1 ratio is advanced evenly to mix with presoma and lithium carbonate in the ratio of the total molal quantity of the molal quantity of lithium and nickel, manganese, copper, with the powder pressing that evenly mixes, 600 ℃ of insulations 20 hours, be warmed up to 1100 ℃ of insulations 4 hours then, obtain lithium-rich manganese-based material Li[Li 0.067Ni 0.3Cu 0.1Mn 0.533] O 2
XRD figure cutting edge of a knife or a sword shape is sharp-pointed, and diffracted intensity height, material have layer structure and crystalline form is complete.
With Li[Li 0.067Ni 0.3Cu 0.1Mn 0.533] O 2For positive electrode is assembled into the AA battery.At 2.5-4.6V, 1C discharges and recharges that specific discharge capacity is 220mAh/g under the condition.
Embodiment 5
With nickel, cobalt, manganese metal ion molar percentage is 0.322: 0.214: 0.464, nickelous sulfate, manganese sulfate, manganese sulfate are dissolved in the deionized water, being made into nickel, cobalt, manganese ion total concentration is the homogeneous transparent solution of 1mol/L, the preparation NaOH of 2mol/L and the ammoniacal liquor mixed solution of 3mol/L are pumped into mixed salt solution and sodium hydroxide solution simultaneously and carry out coprecipitation reaction in the reactor.Precipitated product after filtration, cleaning, drying, obtain metal hydroxides presoma Ni 0.322Co 0.214Mn 0.464(OH) 2
Is that 1.18: 1 ratio is advanced evenly to mix with presoma and lithium carbonate in the ratio of the total molal quantity of the molal quantity of lithium and nickel, manganese, with the powder pressing that evenly mixes, 750 ℃ of insulations 10 hours, be warmed up to 900 ℃ of insulations 30 hours then, obtain lithium-rich manganese-based material Li[Li 0.067Ni 0.3Co 0.2Mn 0.433] O 2
With Li[Li 0.067Ni 0.3Co 0.2Mn 0.433] O 2For positive electrode is assembled into the AA battery.At 2.75-4.2V, specific discharge capacity is 160mAh/g when discharging and recharging under the condition of 1C.

Claims (10)

1. lithium-rich manganese-based anode material, its general formula is:
Li[Li (1-2x)/3Ni x-aM yMn (2-x)/3-b]O 2
Wherein M=Co, Al, Ti, Mg, Cu, 0＜x≤0.5,
When M=Co, Al, 0＜y＜2x, a=b=y/2;
When M=Ti, 0＜y＜(2-x)/3, a=0, b=y;
When M=Mg, Cu, 0＜y＜x, a=y, b=0.
2. lithium-rich manganese-based anode material according to claim 1 is characterized in that: the microstructure of described lithium-rich manganese-based anode material is Li 2MnO 3And LiMO 2Layered composite structure.
3. the preparation method of lithium-rich manganese-based anode material according to claim 1 may further comprise the steps:
A) soluble nickel, manganese, M salt are pressed (x-a): [(2-x)/and 3-b]: the mol ratio of y is dissolved in the deionized water, is mixed with the solution that total concentration is 0.5～4mol/L, wherein, and 0＜x≤0.5, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0;
B) mixed solution of preparation aqueous slkali or alkali and ammoniacal liquor, alkali concn is 1～8mol/L, the ammoniacal liquor molar concentration is 0.1～4mol/L;
C) in reactor, add the deionized water that accounts for reactor total measurement (volume) 10%-30%, described nickel, manganese, M salting liquid are pumped in the reactor, mixed solution with described aqueous slkali or alkali and ammoniacal liquor is pumped in the reactor simultaneously, material in the reactor is stirred, temperature, pH value in the control reactor generate presoma [Ni by coprecipitation reaction (x-a)/(x+ (2-x)/3)M Y/ (x+ (2-x)/3)Mn ((2-x)/3-b)/(x+ (2-x)/3)] (OH) 2Precipitation;
D) presoma is filtered, washing, oven dry back and lithium compound be that { [1+ (1-2x)/3]/[x-a+y+ (2-x)/3-b]+z}: 1 ratio is evenly mixed by the ratio of the total molal quantity of the molal quantity of lithium and nickel, manganese, M, wherein, 0＜x≤0.5,0≤z≤0.1, when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0;
E) homogeneous mixture of presoma and lithium compound is at high temperature fired, promptly obtained Li[Li (1-2x)/3Ni X-aM yMn (2-x)/3-b] O 2Material, wherein M=Co, Al, Ti, Mg, Cu.
4. the preparation method of lithium-rich manganese-based anode material according to claim 3, it is characterized in that: the soluble nickel salt described in the step (a) can be a kind of or its salt-mixture in nickelous sulfate, nickel nitrate, nickel chloride, the nickel acetate; Soluble manganese salt can be a kind of or its salt-mixture in manganese sulfate, manganese nitrate, manganese chloride, the manganese acetate; The solubility cobalt salt can be a kind of or its salt-mixture in cobaltous sulfate, cobalt nitrate, cobalt chloride, the cobalt acetate; Aluminum soluble salt can be a kind of or its salt-mixture in aluminum sulfate, aluminum nitrate, the aluminium chloride; The solubility titanium salt can be a titanium tetrachloride; The solubility magnesium salts can be a kind of or its salt-mixture in magnesium sulfate, magnesium chloride, magnesium nitrate, the magnesium acetate; Soluble copper salt can be a kind of or its salt-mixture in copper sulphate, copper chloride, copper nitrate, the copper acetate.
5. the preparation method of lithium-rich manganese-based anode material according to claim 3, it is characterized in that: the alkali described in the step (b) can be a kind of in NaOH, potassium hydroxide, lithium hydroxide, the sodium carbonate, or the mixture of NaOH, potassium hydroxide, lithium hydroxide, its concentration is 1-8mol/L.
6. the preparation method of lithium-rich manganese-based anode material according to claim 3, it is characterized in that: the nickel described in the step (c), manganese, M solution are to join in the reactor with Sprayable on reactor top, and described aqueous slkali is to feed from the reactor bottom.
7. the preparation method of lithium-rich manganese-based anode material according to claim 3 is characterized in that: the temperature in the reactor described in the step (c) is 40～60 ℃, and the pH value is between 8～12.
8. the preparation method of lithium-rich manganese-based anode material according to claim 3, it is characterized in that: the lithium compound described in the step (d) can be a kind of or its mixture in lithium hydroxide, lithium carbonate, the lithium nitrate, single ratio of planting lithium salts or mixing the total molal quantity of lithium molal quantity total in the lithium salts and nickel, manganese, M is { [1+ (1-2x)/3]/[x-a+y+ (2-x)/3-b]+z}: 1, wherein, 0＜x≤0.5,0≤z≤0.1 is when M=Co, Al, 0＜y＜2x, a=b=y/2; When M=Ti, 0＜y＜(2-x)/3, a=0, b=y; When M=Mg, Cu, 0＜y＜x, a=y, b=0.
9. the preparation method of lithium-rich manganese-based anode material according to claim 3 is characterized in that: the filtration described in the step (d), washing are to make Na in the presoma +, K +Total content is less than 300ppm, and sulfate ion, chloride ion total content are less than 0.5%, and oven dry is to carry out between 80-150 ℃.
10. the preparation method of lithium-rich manganese-based anode material according to claim 3, it is characterized in that: the high-temperature firing described in the step (e), be that heating rate with 1～20 ℃/min is warmed up to 400～800 ℃, insulation 2～20h, and then be warmed up to 800～1100 ℃ with the heating rate of 1～20 ℃/min, insulation 4～40h.
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