CN105322155A - Lithium-rich manganese-based layered composite oxide cathode material, preparation method and application thereof - Google Patents
Lithium-rich manganese-based layered composite oxide cathode material, preparation method and application thereof Download PDFInfo
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- CN105322155A CN105322155A CN201410250712.9A CN201410250712A CN105322155A CN 105322155 A CN105322155 A CN 105322155A CN 201410250712 A CN201410250712 A CN 201410250712A CN 105322155 A CN105322155 A CN 105322155A
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Abstract
The invention discloses a lithium-rich manganese-based layered composite oxide cathode material Li<1+x>Mn<y>Ni<z>Co<1-x-y-z>O2, wherein 0.1 < x <= 0.3, 0.33 <= y <= 0.6, 0 < z <= 0.5 and 1-x-y-z >= 0. The invention also discloses a preparation method of the material, including the steps of: 1) mixing a soluble manganese salt, a soluble nickel salt and a soluble cobalt salt to obtain a salt solution, or mixing the soluble manganese salt and the soluble nickel salt to obtain a salt solution, preparing a soluble precipitation agent into a precipitation agent solution, mixing the salt solution with the precipitation agent solution and carrying out a co-precipitation reaction to obtain a co-precipitate; 2) performing a microwave hydrothermal reaction to the co-precipitate, separating, washing and drying the reaction product to obtain a precursor; and 3) mixing the precursor with a lithium source substance and roasting the mixture in air or oxygen. The cathode material is high in embedding-in and removing rate of lithium ions, is high in crystallization degree, is ordered in crystal arrangement, can greatly increase charging and discharging capacity of lithium ion batteries greatly and can prolong the cyclic service life of the battery.
Description
Technical field
The present invention relates to a kind of lithium-rich manganese-based layered mixed oxide positive electrode, and the preparation method of this positive electrode and purposes, belong to anode material for lithium-ion batteries technical field.
Background technology
Lithium ion battery is a kind of brand-new Green Chemistry energy, has the advantage that voltage is high, the life-span is long, energy density is large compared with traditional nickel-cadmium cell, Ni-MH battery.The quality of lithium ion battery chemical property is relevant to electrode material, the specific capacity of existing negative material is generally at more than 300mAh/g, and the specific capacity of positive electrode only maintains about 150mAh/g, far below negative material, therefore the specific capacity of positive electrode improves the large bottleneck becoming lithium ion battery chemical property and promote.In addition, conventional at present cobalt-lithium oxide (LiCoO
2), nickel oxide lithium (LiNiO
2) and manganese oxide lithium (Li
xmn
2o
4) etc. positive electrode in lithium battery recycles, easily there is capacity attenuation, cause the shortening in lithium ion battery useful life.Based on above-mentioned present situation, high, that capacity is not easily decayed when the recycling positive electrode of preparation specific capacity has become technical field of lithium ion technical barrier urgently to be resolved hurrily.
In order to solve an above-mentioned difficult problem, researcher have devised the polynary transition metal composite positive electrode material of the embedding lithium of novel high-capacity stratiform, as Chinese patent literature CN102054986B discloses ultra-high capacity anode material for lithium-ion batteries prepared by a kind of microwave method and preparation method thereof, positive electrode is Li
1+xni
αco
βmn
γm '
δo
2wherein 0 < x≤0.33,0≤α < 1,0≤β < 1,0 < γ < 1,0≤δ≤0.2 is zero, M ' when α, β are different is one or more elements in Mg, Al, B, Ga, Zr, Ti, Cr, Zn or Fe; Its preparation method is by the hydroxide of certain proportion lithium, oxide or salt, the hydroxide of the hydroxide of transition metal M, oxide or salt and doping metals M ', oxide or salt and additive are mixed by machinery or chemical mode and are placed in air atmosphere stove, adopt microwave heating or microwave and other conventional resistive to heat the mode be combined with each other to heat-treat, obtain required stratiform lithium-rich manganese base oxide and be ultra-high capacity anode material for lithium-ion batteries; M is one or more in nickel, cobalt or manganese.
The stratiform lithium-rich manganese base oxide of above-mentioned technology can be used as positive electrode and uses, but the lithium ion in above-mentioned stratiform lithium-rich manganese base oxide not easily embeds and deviates from, and causes the charge/discharge capacity of lithium ion battery low.
And the grain size of above-mentioned technology positive electrode is uneven, and crystal regularity is poor, and fault in material is more, and in charge and discharge process, positive electrode easily performance degradation occurs.
Summary of the invention
A technical problem to be solved by this invention is that in the stratiform lithium-rich manganese base oxide of prior art, lithium ion not easily embeds and deviates from, and causes the charge/discharge capacity of lithium ion battery low; And then the lithium-rich manganese-based layered mixed oxide positive electrode that a kind of lithium ion easily embeds and deviate from is proposed.
The present invention simultaneously another technical problem to be solved be prior art stratiform lithium-rich manganese base oxide positive electrode grain size heterogeneity, crystal regularity is poor, defect is many, easily performance degradation occurs in charge and discharge process; And then propose that a kind of crystal is regular, performance not easily decays in charge and discharge process lithium-rich manganese-based layered mixed oxide positive electrode.
For solving the problems of the technologies described above, the invention provides a kind of lithium-rich manganese-based layered mixed oxide positive electrode, positive electrode is Li
1+xmn
yni
zco
1-xxy-zo
2, wherein 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z>=0.
The preparation method of described positive electrode, comprises,
(1) mixing soluble manganese salt, soluble nickel salt and soluble cobalt are made into salting liquid or mixing soluble manganese salt and soluble nickel salt and are made into salting liquid, solubility precipitation reagent is made into precipitant solution, mix described salting liquid and precipitant solution carries out coprecipitation reaction, obtain coprecipitate;
(2) described coprecipitate carries out microwave hydrothermal reaction, and product, through being separated, washing and drying, obtains presoma;
(3) described presoma is mixed with lithium source substance, roasting in oxygen-containing atmosphere.
The reaction temperature of described microwave hydrothermal reaction is 150-220 DEG C, and reaction pressure is 1.0-4.0MPa, and the reaction time is 0.5-4h.
The concentration of described precipitant solution is 0.01-3.0mol/L, and in described salting liquid, in metal cation total amount and described precipitant solution, the mol ratio of anion is 1:1.
Described presoma is the micron ball that nanometer sheet is formed, and the particle diameter of described nanometer sheet is 50-100nm, thickness is 10-20nm, and the particle diameter of described micron ball is 1-10um.
The hybrid mode of step (1) is for drip described salting liquid or pump in described precipitant solution and to stir, or described precipitant solution to be dripped or pumps in described salting liquid and to stir, the speed dripped or pump into is 0.005-50ml/min, and mixing speed is 100-1500rpm; The time of coprecipitation reaction is 1-24h, and the temperature of coprecipitation reaction is 25-60 DEG C.
The temperature of described coprecipitation reaction is 45-55 DEG C.
Sintering temperature is 500-1050 DEG C, and roasting time is 5-24h.
Described sintering temperature is 800-950 DEG C, and described roasting time is 10-15h.
Mix described soluble manganese salt, soluble nickel salt, soluble cobalt and surfactant and be made into described salting liquid, or mix described soluble manganese salt, soluble nickel salt and surfactant and be made into described salting liquid.
Described surfactant is polyvinylpyrrolidone; In described salting liquid, the mol ratio of described surfactant and metal cation total amount is 1:(10-50).
With the molar amount of metal cation, the ratio of described soluble manganese salt, soluble nickel salt and soluble cobalt is y:z:(1-x-y-z), wherein 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z >=0.
In described salting liquid, the total concentration of metal cation is 0.01-2.0mol/L.
With the molar amount of metal cation, the ratio of described lithium source substance and soluble cobalt is (1+x): (1-x-y-z), wherein 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z >=0.
Described manganese salt is one or more in manganese nitrate, manganese acetate, manganese chloride and manganese sulfate; Described nickel salt is one or more in nickel nitrate, nickel acetate, nickel chloride and nickelous sulfate; Described cobalt salt is one or more in cobalt nitrate, cobalt acetate, cobalt chloride and cobaltous sulfate; Described lithium source substance is one or more in lithium carbonate, lithium oxalate and lithium hydroxide.
Described precipitation reagent is one or more in carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate and sodium oxalate; Described presoma is Mn
yni
zco
1-x-y-z(CO
3)
1-xor Mn
yni
zco
1-x-y-z(C
2o
4)
1-x, wherein 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z>=0.
Described lithium-rich manganese-based layered mixed oxide positive electrode is used for lithium rechargeable battery.
Reaction principle when adopting carbonate or oxalates to make precipitation reagent is as follows:
Soluble manganese salt, nickel salt, cobalt salt solution are mixed with soluble carbonate salt or oxalate solution, forms suspension-turbid liquid; Then microwave attenuation materials method is utilized to make this suspension-turbid liquid crystallization fast, thus the Mn of height of formation crystallization
yni
zco
1-x-y-z(CO
3)
1-xor Mn
yni
zco
1-x-y-z(C
2o
4)
1-x(wherein: 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z>=0, there is following chemical reaction in it:
yMn
2++zNi
2++(1-x-y-z)Co
2++(1-x)CO
3 2-＝Mn
yNi
zCo
1-x-y-z(CO
3)
1-x
yMn
2++zNi
2++(1-x-y-z)Co
2++(1-x)C
2O
4 2-＝Mn
yNi
zCo
1-x-y-z(C
2O
4)
1-x
The present invention has following beneficial effect compared with prior art:
(1) lithium-rich manganese-based layered mixed oxide positive electrode of the present invention, Li
1+xmn
yni
zco
1-x-y-zo
2, wherein 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z>=0.This material has very high Lithium-ion embeding and extrusion rate, increases the charge/discharge capacity of lithium ion battery.And homogeneous grain size, the crystal regularity of this positive electrode are high, not easily generating material performance degradation in charge and discharge process, can use by iterative cycles.
(2) preparation method of lithium-rich manganese-based layered mixed oxide positive electrode of the present invention, by soluble manganese salt, soluble nickel salt and soluble cobalt are made into after salting liquid or mixing soluble manganese salt and soluble nickel salt are made into salting liquid co-precipitation carries out microwave attenuation materials, obtain homogeneous grain size, the presoma that crystal regularity is high, be mixed in roasting in oxygen-containing atmosphere more namely to obtain stratiform lithium-rich manganese base oxide can be used as positive electrode with lithium source substance, the lithium ion of this positive electrode easily embeds and deviates from, make battery charging and discharging capacity large, and the homogeneous grain size of positive electrode, crystal regularity is high, when discharge and recharge uses, positive electrode is not easily decayed, can use by iterative cycles.
(3) preparation method of lithium-rich manganese-based layered mixed oxide positive electrode of the present invention, the reaction temperature of described microwave hydrothermal reaction is 150-220 DEG C, and reaction pressure is 1.0-4.0MPa, and the reaction time is 0.5-4h; The concentration of described precipitant solution is 0.01-3.0mol/L, and in described salting liquid, in metal cation total amount and described precipitant solution, the mol ratio of anion is 1:1.Ratio, the concentration of above-mentioned microwave hydrothermal reaction condition and coprecipitation reaction thing, presoma is made to be the micron ball that nanometer sheet is formed, the particle diameter of described nanometer sheet is 50-100nm, thickness is 10-20nm, the particle diameter of described micron ball is 1-10um, thus control pattern and the structure of presoma, for the positive electrode obtaining degree of crystallinity further regular is laid a good foundation.
(4) preparation method of lithium-rich manganese-based layered mixed oxide positive electrode of the present invention, sintering temperature is 500-1050 DEG C, and roasting time is 5-24h.After being mixed with lithium source substance by presoma, by controlling heat treated temperature, time, in roasting process, the regularity of presoma can be kept further, thus the positive electrode that final formation crystallization regularity is high; After microwave hydrothermal reaction, introduce lithium source substance and roasting, can improve embedding and the extrusion rate of lithium ion in positive electrode, above-mentioned roasting condition can further improve embedding and the extrusion rate of lithium ion, thus makes lithium-rich manganese-based anode material Li
1+xmn
yni
zco
1-x-y-zo
2electrochemistry can improve further.
(5) preparation method of lithium-rich manganese-based layered mixed oxide positive electrode of the present invention, surfactant can make each metal cation in salting liquid dispersed, obtain the equally distributed coprecipitate of metal ion through co-precipitation again, improve the homogeneous property of final positive electrode.
Accompanying drawing explanation
In order to make content of the present invention more easily be understood, the present invention is further detailed content of the present invention with embodiment by reference to the accompanying drawings;
Fig. 1 is the scanning electron microscope diagram of coprecipitate in the embodiment of the present invention 1;
Fig. 2 is the scanning electron microscope diagram of presoma in the embodiment of the present invention 1;
Fig. 3 is the transmission electron microscope figure of presoma in the embodiment of the present invention 1;
Fig. 4 is the high-resolution-ration transmission electric-lens figure of presoma in the embodiment of the present invention 1;
Fig. 5 is the scanning electron microscope diagram of the embodiment of the present invention 1 positive electrode 1;
Fig. 6 is the high-resolution-ration transmission electric-lens figure of the embodiment of the present invention 1 positive electrode 1;
Fig. 7 is the XRD figure of the embodiment of the present invention 1 positive electrode 1;
Embodiment
Embodiment 1
(1) mix the four nitric hydrate manganese of 18.2g, 6.56g Nickelous nitrate hexahydrate, 1.46g cabaltous nitrate hexahydrate to add water and the PVP adding 0.508g is made into 200ml salting liquid, be placed in the three-necked bottle of 500ml, three-necked bottle is placed in and is heated to 50 DEG C with the oil bath of magnetic stirring apparatus or water-bath, magnetic agitation speed is 1000rpm.The sal soda taking 30.04g (fully precipitates to make metal ion, sodium carbonate excessive 5%) be dissolved in 100ml water, instill in above-mentioned three-necked bottle by constant pressure funnel, within 1 hour, dropwise, then continue to stir 6h, the coprecipitate obtained as shown in Figure 1;
(2) coprecipitate is proceeded to microwave with in high-pressure sealed reactor, then reactor is put into microwave heating system, microwave hydrothermal reaction 2h at 200 DEG C of temperature and 1.5-2.5MPa pressure, product is cooled to room temperature, through centrifugation, water and ethanol replace washing three times, in vacuum drying chamber, dry 10h at 110 DEG C, obtain presoma as in Figure 2-4, adopt ICP-AES analytic approach, and in conjunction with the test of x-ray photoelectron power spectrum, the molecular formula of known presoma is Mn
0.725ni
0.225co
0.05cO
3;
(3) the presoma Mn of 9.36g is taken
0.725ni
0.225co
0.05cO
3mix with a hydronium(ion) lithia of 5.19g, for making up the lithium loss that high―temperature nuclei causes, lithium source excessive 3%, in air atmosphere after 850 DEG C of sintering 10h, obtain positive electrode 1 as illustrated in figs. 5-7, adopt ICP-AES analytic approach, and in conjunction with the test of x-ray photoelectron power spectrum, the molecular formula of known positive electrode 1 is Li
1.2mn
0.58ni
0.18co
0.04o
2.
As shown in Figure 1, coprecipitate is micro-sphere structure, microsphere diameter 2-5um, and this microballoon is formed by nano-particles self assemble, and the particle diameter of nano particle is 1-10nm.
From Fig. 2-4, coprecipitated product is after microwave chemical hydrothermal treatment consists, and micro-sphere structure does not change substantially, but the nano particle forming microballoon but there occurs very large change, become nanometer sheet by nano particle, nanometer sheet particle size is 50-80nm, and thickness is 10-20nm.
From Fig. 5-7, the micro-sphere structure of precursor obtains maintenance substantially, and positive electrode 1 degree of crystallinity is very high.
Embodiment 2
(1) add water after mixing the cobalt nitrate mixing of the manganese nitrate of 3.3mol, the nickel nitrate of 3mol and 1.7mol and be made into salting liquid, in salting liquid, the concentration of manganese ion, nickel ion and cobalt ions total amount is 0.01mol/L, ammonium carbonate is made into 0.01mol/L precipitant solution, isopyknic precipitant solution is added dropwise in salting liquid to be uniformly mixed with the speed of 0.005ml/min and carries out coprecipitation reaction, mixing speed is 500rpm, coprecipitation reaction temperature is 25 DEG C, reaction time is 24h, obtains coprecipitate;
(2) by described coprecipitate microwave hydrothermal reaction 4h at 150 DEG C of temperature and 4.0MPa pressure, product is cooled to room temperature, and through centrifugation, water and ethanol replace washing three times, in vacuum drying chamber, dry 10h at 110 DEG C, obtain presoma Mn
0.33ni
0.2co
0.17(CO
3)
0.7;
(3) after the lithium hydroxide adding 13mol in described presoma carries out ball milling mixing, in air atmosphere, 800 DEG C of roasting 24h, obtain positive electrode 2, its molecular formula is Li
1.3mn
0.33ni
0.2co
0.17o
2.
Embodiment 3
(1) add water after mixing the cobalt acetate mixing of the manganese acetate of 6mol, the nickel acetate of 1mol and 1mol and be made into salting liquid, in salting liquid, the concentration of manganese ion, nickel ion and cobalt ions total amount is 2mol/L, ammonium carbonate is made into 3mol/L precipitant solution, precipitant solution is added dropwise in salting liquid to be uniformly mixed with the speed of 50ml/min and carries out coprecipitation reaction, the volume ratio of precipitant solution and salting liquid is 2:3, mixing speed is 1500rpm, coprecipitation reaction temperature is 60 DEG C, reaction time is 1h, obtains coprecipitate;
(2) by described coprecipitate microwave hydrothermal reaction 0.5h at 220 DEG C of temperature and 2.0MPa pressure, product is cooled to room temperature, and through centrifugation, deionized water, ethanol replace washing three times, in vacuum drying chamber, dry 15h at 120 DEG C, obtain presoma Mn
0.6ni
0.1co
0.1(CO
3)
0.8;
(3) after the lithium oxalate adding 6mol in described presoma carries out mechanical mixture, in oxygen atmosphere, 1050 DEG C of roasting 5h, obtain positive electrode 3, its molecular formula is Li
1.2mn
0.6ni
0.1co
0.1o
2.
Embodiment 4
(1) manganese chloride of 2mol is mixed, the manganese nitrate of 1.3mol, the nickel chloride of 3mol, to add water after the cobalt chloride mixing of the nickel nitrate of 2mol and 0.5mol and the PVP adding 85g is made into salting liquid, manganese ion in salting liquid, the concentration of nickel ion and cobalt ions total amount is 1mol/L, sodium carbonate is made into 1mol/L precipitant solution, isopyknic precipitant solution is added dropwise in salting liquid to be uniformly mixed with the speed of 20ml/min and carries out coprecipitation reaction, mixing speed is 1000rpm, coprecipitation reaction temperature is 45 DEG C, reaction time is 20h, obtain coprecipitate,
(2) by described coprecipitate microwave hydrothermal reaction 2h at 200 DEG C of temperature and 3.0MPa pressure, product is cooled to room temperature, and through centrifugation, acetone replaces washing three times, in vacuum drying chamber, dry 10h at 120 DEG C, obtains presoma Mn
0.33ni
0.5co
0.05(CO
3)
0.88;
(3), after the lithium carbonate adding 5.6mol in described presoma carries out mechanical mixture, at air atmosphere, 950 DEG C of roasting 10h, obtain positive electrode 4, its molecular formula is Li
1.12mn
0.33ni
0.5co
0.05o
2.
Embodiment 5
(1) to add water after mixing the cobaltous sulfate mixing of the manganese sulfate of 5mol, the nickelous sulfate of 1mol, 2mol and the PVP adding 120g is made into salting liquid, in salting liquid, the concentration of manganese ion, nickel ion and cobalt ions total amount is 1.5mol/L, sodium oxalate is made into 1.5mol/L precipitant solution, isopyknic precipitant solution is added dropwise in salting liquid to be uniformly mixed with the speed of 30ml/min and carries out coprecipitation reaction, mixing speed is 1000rpm, coprecipitation reaction temperature is 55 DEG C, reaction time is 20h, obtains coprecipitate;
(2) by described coprecipitate microwave hydrothermal reaction 2h at 200 DEG C of temperature and 3.0MPa pressure, product is cooled to room temperature, and through centrifugation, acetone replaces washing three times, in vacuum drying chamber, dry 10h at 120 DEG C, obtains presoma Mn
0.5ni
0.1co
0.2(C
2o
4)
0.8;
(3), after the lithium carbonate of the lithium oxalate and 3mol that add 3mol in described presoma carries out mechanical mixture, at air atmosphere, 800 DEG C of roasting 15h, obtain positive electrode 5, its molecular formula is Li
1.2mn
0.5ni
0.1co
0.2o
2.
Embodiment 6
(1) mix the four nitric hydrate manganese of 18.2g, 5.09g Nickelous nitrate hexahydrate, 2.91g cabaltous nitrate hexahydrate to add water and the PVP adding 1.043g is made into 200ml salting liquid, be placed in the three-necked bottle of 500ml, three-necked bottle is placed in and is heated to 50 DEG C with the oil bath of magnetic stirring apparatus or water-bath, magnetic agitation speed is 1000rpm.The sal soda (in order to make metal ion fully precipitate, sodium carbonate excessive 5%) taking 30.04g is dissolved in 100ml water, instills in above-mentioned three-necked bottle, within 1 hour, dropwise by constant pressure funnel, then continues to stir 6h, obtains coprecipitate;
(2) described coprecipitate is proceeded to microwave with in high-pressure sealed reactor, then reactor is put into microwave heating system, microwave hydrothermal reaction 2h at 200 DEG C of temperature and 1.5-2.5MPa pressure, product is cooled to room temperature, through centrifugation, water and ethanol replace washing three times, in vacuum drying chamber, dry 10h at 110 DEG C, obtain presoma Mn
0.725ni
0.175co
0.1cO
3;
(3) the presoma Mn of 9.36g is taken
0.725ni
0.175co
0.1cO
3mix with a hydronium(ion) lithia of 5.19g, for making up the lithium loss that high―temperature nuclei causes, lithium source excessive 3%, in air atmosphere after 900 DEG C of sintering 10h, obtain positive electrode 6, its molecular formula is Li
1.2mn
0.58ni
0.14co
0.08o
2.
Embodiment 7
(1) mix the four nitric hydrate manganese of 18.2g, 7.8g Nickelous nitrate hexahydrate adds water and the PVP adding 1.05g is made into 200ml salting liquid, be placed in the three-necked bottle of 500ml, three-necked bottle is placed in and is heated to 50 DEG C with the oil bath of magnetic stirring apparatus or water-bath, magnetic agitation speed is 1000rpm.The sal soda (in order to make metal ion fully precipitate, sodium carbonate excessive 5%) taking 30.04g is dissolved in 100ml water, instills in above-mentioned three-necked bottle, within 1 hour, dropwise by constant pressure funnel, then continues to stir 6h, obtains coprecipitate;
(2) described coprecipitate is proceeded to microwave with in high-pressure sealed reactor, then reactor is put into microwave heating system, microwave hydrothermal reaction 2h at 200 DEG C of temperature and 1.5-2.5MPa pressure, product is cooled to room temperature, through centrifugation, water and ethanol replace washing three times, in vacuum drying chamber, dry 10h at 110 DEG C, obtain presoma Mn
0.725ni
0.275cO
3;
(3) the presoma Mn of 9.38g is taken
0.725ni
0.275cO
3mix with a hydronium(ion) lithia of 5.21g, for making up the lithium loss that high―temperature nuclei causes, lithium source excessive 3%, in air atmosphere after 850 DEG C of sintering 10h, obtain positive electrode 7, its molecular formula is Li
1.2mn
0.58ni
0.22o
2.
Embodiment 8
(1) mix the four nitric hydrate manganese of 1.82kg, 0.656kg Nickelous nitrate hexahydrate, 0.146kg cabaltous nitrate hexahydrate to add water and the PVP of the 0.051kg added is made into 10L salting liquid, the sal soda taking 3.01kg (fully precipitates to make metal ion, sodium carbonate excessive 5%) soluble in water, be made into 10L precipitant solution.Utilize 10L coprecipitation reaction still, by peristaltic pump, above-mentioned two kinds of solution being pumped into reactor interior reaction temperature with the speed of 20ml/min is 50 DEG C, and mixing speed is 1000 revs/min, all pumps into rear continuation and stirs 6h, obtain coprecipitate;
(2) described coprecipitate is proceeded to microwave with in high-pressure sealed reactor, then reactor is put into microwave heating system, microwave hydrothermal reaction 2h at 200 DEG C of temperature and 1.5-2.5MPa pressure, product is cooled to room temperature, through centrifugation, water and ethanol replace washing three times, in vacuum drying chamber, dry 10h at 110 DEG C, obtain presoma Mn
0.725ni
0.225co
0.05cO
3;
(3) the presoma Mn of 0.936kg is taken
0.725ni
0.225co
0.05cO
3mix with a hydronium(ion) lithia of 0.519kg, for making up the lithium loss that high―temperature nuclei causes, lithium source excessive 3%, in air atmosphere after 900 DEG C of sintering 10h, obtain positive electrode 8, its molecular formula is Li
1.2mn
0.58ni
0.18co
0.04o
2.
Comparative example
With the mixed in molar ratio that potassium hydroxide, oxalic acid, nickel acetate, cobalt acetate, manganese acetate are 1.21:2:0.13:0.13:0.54, (rotating speed is 500rppm, Ball-milling Time 3h to carry out dry ball milling.Ratio of grinding media to material is 10:1).Then gained powder is placed in Isothermal sinter 1h at microwave air atmosphere furnace 400 DEG C, then Isothermal sinter 0.5h at 800 DEG C, naturally cool to room temperature and obtain stratiform lithium-rich manganese base oxide positive electrode A, its molecular formula is Li
1.2mn
0.54ni
0.13co
0.13o
2.
Test case
The manufacture method of positive plate is: mixed by the weight ratio of 80:10:10 with acetylene black, PVDF respectively by the positive electrode of embodiment 1-8 and comparative example, add solvent, make anode sizing agent, be uniformly coated on aluminium foil, and dry also rolling, makes positive plate.Barrier film is PE barrier film.In argon gas glove box, successively positive plate, barrier film, lithium sheet, nickel foam will be put into R2025 button cell housing, and inject electrolyte, with sealing machine, button cell is sealed, make lithium ion battery.
1. charge-discharge property test:
Performance of lithium ion battery test cabinet is adopted to test, with the electric current of 25mA/g first by each constant-current charging of battery to 4.7V, then with 25mA/g by battery constant-current discharge to 2.0V, record discharge capacity first, according to first discharge specific capacity=discharge capacity/positive plate quality, obtain first discharge specific capacity, the results are shown in Table 1.
Table 1
As shown in Table 1, positive electrode 1-8 makes the first discharge specific capacity of made lithium ion battery 1-8 be greater than the lithium ion battery A of comparative example, this mainly easily embeds due to lithium ion in positive electrode 1-8 of the present invention and deviates from, thus substantially increases the chemical property of lithium ion battery.
2. high rate performance and cycle performance test:
Performance of lithium ion battery test cabinet is adopted to carry out multiplying power discharging test respectively to lithium ion battery 1-8 and A after completing first charge-discharge, with discharge capacity first for battery rated capacity; Used by battery 0.2C/0.5C/1C constant current charge to 4.7V respectively, then constant voltage charge under 4.7V, cut-off current is 0.02C, correspondingly be discharged to 2.0V with 0.2C/0.5C/1C respectively again, record discharge capacity during 0.2C/0.5C/1C discharge and recharge respectively, according to specific discharge capacity=discharge capacity/positive plate quality, obtain specific discharge capacity during 0.2C/0.5C/1C discharge and recharge, the results are shown in Table 2;
By lithium ion battery 1-8 and A according to said process respectively 0.2C discharge and recharge 100 times, record initial discharge capacity and 100 times after discharge capacity, calculated capacity conservation rate, the results are shown in Table 2;
Discharge capacity/initial discharge capacity × 100% behind capability retention=100th time
Table 2
As shown in Table 2, the specific discharge capacity of the lithium ion battery made by positive electrode 1-8 under 0.2C/0.5C/1C is all greater than the lithium ion battery of positive electrode A; And it is more than 90% that the lithium ion battery made by positive electrode 1-8 recycles the capability retention after 100 times, higher than the lithium ion battery of positive electrode A, positive electrode 1-8 of the present invention not easily generating material performance degradation in battery use procedure is described.
Although the present invention has carried out detailed elaboration by above-mentioned specific embodiment to it; but; those skilled in the art should be understood that and made on this basis not exceed any form of claims and the change of details, all belong to invention which is intended to be protected.
Claims (17)
1. a lithium-rich manganese-based layered mixed oxide positive electrode, is characterized in that, positive electrode is Li
1+xmn
yni
zco
1-x-y-zo
2, wherein 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z>=0.
2. the preparation method of positive electrode described in claim 1, comprises,
(1) mixing soluble manganese salt, soluble nickel salt and soluble cobalt are made into salting liquid or mixing soluble manganese salt and soluble nickel salt and are made into salting liquid, solubility precipitation reagent is made into precipitant solution, mix described salting liquid and precipitant solution carries out coprecipitation reaction, obtain coprecipitate;
(2) described coprecipitate carries out microwave hydrothermal reaction, and product, through being separated, washing and drying, obtains presoma;
(3) described presoma is mixed with lithium source substance, roasting in oxygen-containing atmosphere.
3. preparation method according to claim 2, is characterized in that, the reaction temperature of described microwave hydrothermal reaction is 150-220 DEG C, and reaction pressure is 1.0-4.0MPa, and the reaction time is 0.5-4h.
4. the preparation method according to Claims 2 or 3, is characterized in that, the concentration of described precipitant solution is 0.01-3.0mol/L, and in described salting liquid, in metal cation total amount and described precipitant solution, the mol ratio of anion is 1:1.
5., according to the arbitrary described preparation method of claim 2-4, it is characterized in that, described presoma is the micron ball that nanometer sheet is formed, and the particle diameter of described nanometer sheet is 50-100nm, thickness is 10-20nm, and the particle diameter of described micron ball is 1-10um.
6. according to the arbitrary described preparation method of claim 2-5, it is characterized in that, the hybrid mode of step (1) is for drip described salting liquid or pump in described precipitant solution and to stir, or described precipitant solution to be dripped or pumps in described salting liquid and to stir, the speed dripped or pump into is 0.005-50ml/min, and mixing speed is 100-1500rpm; The time of coprecipitation reaction is 1-24h, and the temperature of coprecipitation reaction is 25-60 DEG C.
7. preparation method according to claim 6, is characterized in that, the temperature of described coprecipitation reaction is 45-55 DEG C.
8., according to the arbitrary described preparation method of claim 2-7, it is characterized in that, sintering temperature is 500-1050 DEG C, and roasting time is 5-24h.
9. preparation method according to claim 8, is characterized in that, described sintering temperature is 800-950 DEG C, and described roasting time is 10-15h.
10. according to the arbitrary described preparation method of claim 2-9, it is characterized in that, mix described soluble manganese salt, soluble nickel salt, soluble cobalt and surfactant and be made into described salting liquid, or mix described soluble manganese salt, soluble nickel salt and surfactant and be made into described salting liquid.
11. preparation methods according to claim 10, is characterized in that, described surfactant is polyvinylpyrrolidone; In described salting liquid, the mol ratio of described surfactant and metal cation total amount is 1:(10-50).
12. according to the arbitrary described preparation method of claim 2-11, it is characterized in that, with the molar amount of metal cation, the ratio of described soluble manganese salt, soluble nickel salt and soluble cobalt is y:z:(1-x-y-z), wherein 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z >=0.
13. according to the arbitrary described preparation method of claim 2-12, and it is characterized in that, in described salting liquid, the total concentration of metal cation is 0.01-2.0mol/L.
14. according to the arbitrary described preparation method of claim 2-13, it is characterized in that, with the molar amount of metal cation, the ratio of described lithium source substance and soluble cobalt is (1+x): (1-x-y-z), wherein 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z >=0.
15., according to the arbitrary described preparation method of claim 2-14, is characterized in that, described manganese salt is one or more in manganese nitrate, manganese acetate, manganese chloride and manganese sulfate; Described nickel salt is one or more in nickel nitrate, nickel acetate, nickel chloride and nickelous sulfate; Described cobalt salt is one or more in cobalt nitrate, cobalt acetate, cobalt chloride and cobaltous sulfate; Described lithium source substance is one or more in lithium carbonate, lithium oxalate and lithium hydroxide.
16., according to the arbitrary described preparation method of claim 2-15, is characterized in that, described precipitation reagent is one or more in carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate and sodium oxalate; Described presoma is Mn
yni
zco
1-x-y-z(CO
3)
1-xor Mn
yni
zco
1-x-y-z(C
2o
4)
1-x, wherein 0.1 < x≤0.3,0.33≤y≤0.6,0<z≤0.5 and 1-x-y-z>=0.
Layered mixed oxide positive electrode lithium-rich manganese-based described in claim 1 is used for lithium rechargeable battery by 17..
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