CN102332585A - Lithium nickel cobalt manganese oxygen/stannic oxide composite anode material doped with metal elements and method for preparing lithium nickel cobalt manganese oxygen/stannic oxide composite anode material - Google Patents
Lithium nickel cobalt manganese oxygen/stannic oxide composite anode material doped with metal elements and method for preparing lithium nickel cobalt manganese oxygen/stannic oxide composite anode material Download PDFInfo
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Abstract
The invention relates to the technical field of electrode materials of lithium ion batteries and preparation of the electrode materials, in particular to a lithium nickel cobalt manganese oxygen/stannic oxide composite anode material doped with metal elements and a method for preparing the lithium nickel cobalt manganese oxygen/stannic oxide composite anode material. The lithium nickel cobalt manganese oxygen/stannic oxide composite anode material doped with the metal elements is expressed by LiNixCoyMnzRzO2/SnO2 and obtained by performing high-temperature solid-phase reaction on nickel, cobalt and manganese compounds, lithium salt, doped metal compounds and stannic compounds. By doping the metal elements and coating the stannic oxide, the initial discharge capacity, multiplying power performance and cycle stability of the material can be effectively improved. The material is prepared by using all-solid-phase reaction, and the process is simple in flow and convenient to operate.
Description
Technical field
The present invention relates to lithium ion battery electrode material and preparing technical field thereof, particularly, relate to lithium nickel cobalt manganese oxygen/tin oxide composite positive pole of a kind of doped metallic elements and preparation method thereof.
Background technology
Lithium ion battery is a kind of commercial rechargeable battery that recent two decades just grows up, and it mainly relies on lithium ion between positive pole and negative pole, to move work.Because characteristics such as it has the energy density height, have extended cycle life, environmentally friendly; So far progressively substitute traditional lead acid accumulator, Ni-MH battery etc., be widely used as the supporting power supply of portable electric appts such as mobile phone, digital camera, notebook computer and electric tool, electric automobile etc.Lithium ion battery mainly is made up of positive electrode, barrier film, negative material and electrolyte, and why existing commercialization lithium ion battery has outstanding energy advantage, mainly has benefited from its negative material (LiC
6/ C) the advantage of electronegative potential and high power capacity, the electronegative potential of negative pole is brought into play the high voltage of positive electrode fully, and simultaneously, negative pole also makes positive electrode become the key factor that restriction lithium ion battery overall performance further improves far above the capacity of positive pole.Therefore, the research of positive electrode receives increasing attention.
In recent years, the stratiform anode material for lithium-ion batteries is the focus of research in the field.In existing stratiform anode material for lithium-ion batteries, LiCoO
2In compact battery, be used widely, but because of overcharging restriction, its specific energy does not far reach theoretical capacity, and receive the restriction of cobalt resource; Stratiform LiMnO
2Very high embedding lithium capacity is arranged, but crystal structure is prone to subside in the cycle charge discharge electric process, causes capacity to descend the cycle performance variation; LiNiO
2Then synthetic difficulty overcharges poor stability.Therefore, become the focus of international chemical power source circle from the ideal electrode active material of resource, environmental protection and security performance aspect searching lithium ion battery.Polynary transiting metal nickel cobalt manganese composite lithium-inserting oxide LiNi
xCo
yMn
L-x-yO
2, because it has Ni-Co-Mn element cooperative effect, chemical property is superior to arbitrary one pack system oxide, causes extensive concern.
Nickel-cobalt-manganese ternary system (Li (Ni, Co, Mn) O
2) the concentrated research of material starts from calendar year 2001; T.Ohzuku and Y.Makimura (Chemistry Letters; 2001,7:642-643.) studied and utilize high temperature solid-state method at 1000 ℃ of following sintering 15h (air atmosphere), synthesized stratiform α-NaFeO first with premium properties
2The nickel-cobalt-manganese ternary of structure is positive electrode LiCo
1/3Ni
1/3Mn
1/3O
2And investigate its chemical property.Though LiNi
1/3Co
1/3Mn
1/3O
2Search time is not long, but because of itself and LiCoO
2Has analog structure, so possess research basis preferably.
CN 1838453A discloses a kind of lithium ion battery anode material lithium nickel cobalt manganese oxygen-Fu lithium type layer structure lithium ion battery positive electrode, and its chemical molecular formula is: Li
L+ δNi
xCo
yMn
zO
2, 1.02＜l+ δ＜2,0.5＜x+y+z＜1 wherein.Its preparation method comprises preparation, nickel, cobalt, the co-precipitation of manganese mixing salt solution, the heat treatment of cobalt-nickel-manganese oxide compound.Adopt the present invention, the cost of raw material is merely LiCoO
2About 1/3; Can obtain the equally distributed precursor of nickel cobalt manganese molecular level, can obtain the high density type spherical precursor, thereby improve the volume of battery energy density; Technological operation is simple with control.With traditional LiCoO
2The work potential scope (2.75-4.3V) of material is compared, and lithium nickel cobalt manganese oxygen positive electrode of the present invention can (2.75-4.6V) is reversible in the potential range of broad discharges and recharges, and has higher specific capacity.
Ternary system (Li (Ni, Co, Mn) O
2) material have the reversible specific capacity higher than cobalt acid lithium (170～200mAh/g), can better meet the electronic product requirement of miniaturization and multifunction day by day.Chemical property such as reversible specific capacity, cycle performance, multiplying power property, overcharging resisting performance, structural stability and the thermal stability etc. of this material are at home and abroad approved widely at present.Because a large amount of comparatively cheap manganese of price and nickel of adopting replace resource shortage and the higher cobalt of price in this material, so the cost of material can have tangible reduction than cobalt acid lithium.But, to compare with traditional lithium cobaltate cathode material, the tap density of this material is on the low side, and the electrode processing characteristics is relatively poor.In order to improve single stratiform LiMeO
2(Me=Co, Mn, Ni) material poor heat stability and in charge and discharge process, change to spinel structure and cause shortcomings such as its cycle performance is relatively poor from layer structure; The researcher begins to utilize element doping that it is carried out the modification processing, partly substitutes LiMeO as using elements such as Ti, Mg, Al, Ga, Fe, Cu, Zn
2In transition metal, obtain Li
1-xMe
xO
2Solid solution stratiform compound.But discover that single element doping is merely able to improve material LiMeO
2Performance in a certain respect as improving its discharge capacity first, but can't realize the comprehensive improvement of performance.
CN 1821163A discloses a kind of lithium ion battery doping with anode material and preparation method thereof, and the material general formula is: Li
xNi
1-y-z-i-jCo
yMn
zNb
iM
jO
2, 0.8≤x≤1.5,0＜y≤0.3,0＜z≤0.5,0＜i≤0.1,0＜j≤0.1 wherein, M represents one or more in molybdenum, strontium, tungsten, vanadium, copper, titanium, the barium element.The preparation method is: get lithium compound, cobalt/cobalt oxide, nickel compound and mix with gas blowout formula dispensing equipment; In negative pressure high frequency vortex centrifugal mix grinding jar, behind the mix grinding, smash the hole, at 600 ℃-1000 ℃ intermittently logical down oxygen roasting 10h-30h through compacting; Obtain intermediate behind the natural cooling; Through pulverizing, grinding, the compound with lithium, manganese, niobium, M carries out negative pressure high frequency vortex centrifugal mix grinding again, smashes the hole through compacting again then; At 500 ℃-900 ℃ intermittently logical down oxygen roasting 4h-30h, promptly obtain target product after the grinding.This positive electrode has characteristics such as high-purity, high crystalline, high battery capacity and structural stability, and security performance is good, memory-less effect.It is short that its preparation method has the reaction time, and production cost is low, is easy to the characteristics of industrialization.
CN 1763996A provides a kind of lithium nickel cobalt manganese composite oxide positive pole material Li through doping vario-property
y(NiCoMn)
1/3-xM
3xO
2(wherein M=Cr, Al and Mg, 0≤x≤0.10,0≤y≤1) and manufacturing approach thereof: with a kind of compound that contains lithium, nickeliferous compound, contain cobalt compound, contain the compound of manganese and contain the compound of chromium or the compound that contains the compound of aluminium or contain magnesium mixes in proportion; Place mortar, after grinding a period of time, add proper amount of deionized water or other suitable solvent; Continue to be ground to the solid material particle and become uniform rheology attitude with Liquid Distribution, after 100 ℃～150 ℃ following dryings are removed moisture, grind a little then, ground raw material; Place Muffle furnace, under air atmosphere, 300 ℃～500 ℃ roastings 3～8 hours; Obtain a presoma; Be transferred in the crucible after this presoma fully ground, sintering 10～30 hours in 700 ℃～1000 ℃ air promptly obtains product again.
D.C.Li (J.PowerSource, 2006,160:1342-1348) and Y.Kim (Electrochimica Acta, 2006,52:1316-1322) wait and to have studied ZrO through spray drying process and sol-gel process
2, TiO
2And Al
2O
3Coating to material at LiNi
1/3Co
1/3Mn
1/3O
2Influence.The coating of these oxides can stop the charge and discharge process middle impedance to become big, improves the high rate performance and the cyclical stability of material.
In the prior art, the ternary system of element doping (Li (Ni, Co, Mn) O
2) positive electrode is difficult in discharge capacity first, the impedance in the charge and discharge process, high rate performance comprehensively improves with the aspects such as cyclical stability under the big electric current.Simultaneously, prior art adopts coprecipitation to prepare positive electrode more, and control requires harshness to conditions such as solution PH, concentration, temperature, mixing speeds in preparation precursor process, in the preparation process, can cause environmental pollution.
Summary of the invention
To the deficiency of prior art, one of the object of the invention has been to provide a kind of lithium nickel cobalt manganese oxygen/tin oxide composite positive pole of doped metallic elements.
According to the lithium nickel cobalt manganese oxygen/tin oxide composite positive pole of doped metallic elements of the present invention, its chemical expression is: LiNi
xCo
yMn
zR
zO
2/ SnO
2, wherein x, y, z, z are respectively the mol ratios of nickel, cobalt, manganese, doped metallic elements.Wherein, 0.1≤x≤0.7,0.1≤y≤0.7,0.1≤z≤0.7,0.001≤z '≤0.2, said x+y+z+z '=1.
As preferred version, 0.15≤x≤0.6,0.15≤y≤0.6,0.15≤z≤0.6,0.005≤z '≤0.15, said x+y+z+z '=1.
Further preferred, 0.15≤x≤0.5,0.15≤y≤0.5,0.15≤z≤0.5,0.005≤z '≤0.15, said x+y+z+z '=1.
Preferred especially, 0.2≤x≤0.4,0.2≤y≤0.4,0.2≤z≤0.4,0.005≤z '≤0.1, said x+y+z+z '=1.
Preferred said doped metallic elements is any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, vanadium, barium, germanium, indium, tantalum, tin or the rare earth element; Be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, vanadium, barium, the tin; Further be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, the tin, be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, the chromium especially.
One of the object of the invention also is to provide a kind of preparation method of lithium nickel cobalt manganese oxygen/tin oxide composite positive pole of doped metallic elements.
The preparation method of the lithium nickel cobalt manganese oxygen of said a kind of doped metallic elements/tin oxide composite positive pole may further comprise the steps:
(1) with the compound of nickel, cobalt, manganese, lithium salts and doping metals compound mix, and again the mixture that obtains are carried out high temperature solid state reaction, obtain the lithium nickel cobalt manganese oxygen composite positive pole of doped metallic elements;
Carry out high temperature solid state reaction again after the lithium nickel cobalt manganese oxygen composite positive pole of the doped metallic elements that (2) step (1) is obtained and tin metal compound mix, obtain the lithium nickel cobalt manganese oxygen/tin oxide composite positive pole of doped metallic elements.
As preferred version, said preparation method may further comprise the steps:
(1) with the compound of nickel, cobalt, manganese; Lithium salts and doping metals compound with the dry materials behind the mixing, are warming up to 500 ℃～1300 ℃ and be incubated and carry out high temperature solid state reaction more than the 3h; Cool off, make the lithium nickel cobalt manganese oxygen composite positive pole of doped metallic elements;
(2) with the lithium nickel cobalt manganese oxygen composite positive pole and the 1wt%～25wt% tin metal compound of 75wt%～99wt% doped metallic elements; Behind the dry materials behind the mixing; Be warming up to 500 ℃～1300 ℃; Carry out high temperature solid state reaction more than the insulation 2h, cool off, make the lithium nickel cobalt manganese oxygen/tin oxide composite positive pole of doped metallic elements.
Preferably, mix the dry afterwards ball milling that carries out before described in the step (1).
Preferably, ball milling described in the step (1) is specially and adds the mix grinding medium and carry out ball milling.
Preferably, ball milling speed is more than the 100rpm described in the step (1), further is preferably more than the 200rpm, is preferably 200rpm～500rpm especially; The preferred said ball milling time is more than the 8h, further is preferably more than the 12h, is preferably 12h～24h especially.
Preferably, in the step (1), the solid content of the mixture of said adding mix grinding medium is 50wt%～90wt%, is preferably 60wt%～80wt% especially.
Preferably, in the step (1), said drying further is preferably 40 ℃～120 ℃ oven dry for oven dry, more preferably 40 ℃～100 ℃ oven dry, is preferably especially 60 ℃～70 ℃ oven dry.
Preferably, in the step (1), said heating rate be 2 ℃/more than the min, further be preferably 5 ℃/more than the min, be preferably 5 ℃/min～10 ℃/min especially.
Preferably, in the step (1), said high temperature solid state reaction temperature is 600 ℃～1200 ℃, more preferably 700 ℃～1100 ℃, is preferably 800 ℃～1050 ℃ especially.
Preferably, in the step (1), the said high temperature solid state reaction time is more than the 5h, further is preferably 5h～25h, is preferably 5h～20h especially.
Preferably, in the step (1), the said natural cooling that is cooled to further is preferably and naturally cools to room temperature.
Preferably, in the step (1), in the lithium nickel cobalt manganese oxygen composite positive pole of said doped metallic elements, the molal quantity of lithium approximates doped metallic elements, nickel, cobalt, manganese total mole number.
Preferably, in the step (2), the addition of the lithium nickel cobalt manganese oxygen composite positive pole of doped metallic elements is the 80wt%～99wt% of the mixture gross mass that obtains, further is preferably 85wt%～97wt%, is preferably 90wt%～95wt% especially; The addition of tin metal compound is preferably the 1wt%～20wt% of the mixture gross mass that obtains, and further is preferably 3wt%～15wt%, is preferably 5wt%～10wt% especially.
Preferably, mix the dry afterwards ball milling that carries out before described in the step (2).
Preferably, ball milling described in the step (2) is specially and adds the mix grinding medium and carry out ball milling.
Preferably, the solid content that adds the mixture of mix grinding medium described in the step (2) is 70wt%～95wt%, is preferably 80wt%～90%wt% especially.
Preferably, in the step (2), said ball milling speed is more than the 100rpm, further is preferably more than the 200rpm, is preferably 200rpm～400rpm especially; The preferred spheres time consuming further is preferably more than the 6h for more than the 4h, more preferably more than the 8h, is preferably 8h～16h especially.
Preferably, in the step (2), said drying further is preferably 40 ℃～120 ℃ oven dry for oven dry, more preferably 40 ℃～100 ℃ oven dry, is preferably especially 60 ℃～70 ℃ oven dry.
Preferably, in the step (2), heating rate be 2 ℃/more than the min, further be preferably 5 ℃/more than the min, be preferably 5 ℃/min～10 ℃/min especially.
Preferably, in the step (2), the high temperature solid state reaction temperature is 500 ℃～1200 ℃, further is preferably 600 ℃～1100 ℃, is preferably 700 ℃～1000 ℃ especially.
Preferably, in the step (2), the high temperature solid state reaction time is more than the 3h, further is preferably 4h～10h, is preferably 4h～6h especially.
Preferably, in the step (2), the said natural cooling that is cooled to further is preferably and naturally cools to room temperature.
Preferably, said mix grinding medium is water, C
1-C
10Alcohol, C
3-C
10Ketone or its mixture, further be preferably water, C
1-C
5Alcohol, C
3-C
5Ketone or its mixture, be preferably deionized water, ethanol and acetone or its mixture especially.
The compound of preferred said nickel, cobalt, manganese comprises nitrate, carbonate, acetate, citrate, sulfate, oxalates, formates or nickel, cobalt, manganese hydroxide and nickel, the cobalt of nickel, cobalt, manganese, in the Mn oxide one or more, and further the compound of preferred said nickel, cobalt, manganese comprises one or more in nitrate, carbonate, acetate, citrate, sulfate or the nickel of nickel, cobalt, manganese, cobalt, manganese hydroxide and nickel, cobalt, the Mn oxide.
Preferred said lithium salts comprises one or more in nitrate, carbonate, acetate, citrate, sulfate, oxalates, formates or the lithium hydroxide of lithium, and further preferred said lithium salts comprises one or more in nitrate, carbonate, acetate, citrate, sulfate or the lithium hydroxide of lithium.
Preferred said doping metals compound comprises nitrate, carbonate, acetate, citrate, sulfate, oxalates, formates or the doping metals hydroxide of doping metals, in the blended metal oxide one or more, and further preferred said doping metals compound comprises nitrate, carbonate, acetate, citrate, sulfate or the doping metals hydroxide of doping metals, in the blended metal oxide one or more.
Preferred said doped metallic elements is any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, vanadium, barium, germanium, indium, tantalum, tin or the rare earth element; Be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, vanadium, barium, the tin; Further be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, the tin, be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, the chromium especially.
Preferred especially said blended metal oxide comprises one or more in titanium dioxide, aluminium oxide, magnesia, cupric oxide, zirconia, silica, the chromium oxide.
Preferred said tin metal compound comprises one or more in nitrate, carbonate, acetate, citrate, sulfate, oxalates, formates or the tin oxide of tin, and further preferred said tin metal compound comprises one or more in nitrate, carbonate, acetate, citrate, sulfate or the tin oxide of tin.
The invention has the beneficial effects as follows:
(1) the present invention is directed to ternary layered positive electrode LiNi
xCo
yMn
L-x-yO
2The problem of high rate performance and cycle performance difference; Lithium nickel cobalt manganese oxygen/tin oxide composite positive pole of a kind of doped metallic elements and preparation method thereof is provided; Wherein doped metallic elements can improve the discharge capacity first of material; Simultaneous oxidation tin coats and can stop the charge and discharge process middle impedance to become big, improves the high rate performance of material and the cyclical stability under the big electric current.
(2) the present invention adopts full solid phase reaction preparation; Can avoid coprecipitation condition controls such as solution PH, concentration, temperature, mixing speed in preparation precursor process to require the environmental pollution that causes in harsh drawback and the preparation process, the cost of material is low for this method, technological process is simple.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment 1
(1) with 0.3 mole of NiO, 0.15 mole of Co
2O
3, 0.3 mole of MnO
2, 0.52 mole of Li
2CO
3With 0.1 mole of SnCO
3Mix and add the 60mL absolute ethyl alcohol and carry out ball milling, ball milling speed 500rpm, ball milling time 20h.Material behind the mixing 70 ℃ of oven dry, is warming up to 800 ℃ and be incubated 20h with the heating rate of 5 ℃/min again, naturally cools to room temperature and make Li (Ni
1/3Co
1/3Mn
1/3)
0.9Sn
0.1O
2Composite positive pole;
(2) with 1g Li (Ni
1/3Co
1/3Mn
1/3)
0.9Sn
0.1O
2Composite positive pole and 0.05g SnO
2Mix, add the 10mL absolute ethyl alcohol and carry out ball milling, ball milling speed 200rpm, ball milling time 16h.After 60 ℃ of oven dry, the heating rate with 5 ℃/min is warming up to 700 ℃ again with the material behind the mixing, and insulation 6h naturally cools to room temperature and makes Li (Ni
1/3Co
1/3Mn
1/3)
0.9Sn
0.1O
2/ SnO
2Composite positive pole.
The manganese of embodiment 1 preparation is mixed and manganese dioxide covered iron lithium phosphate compound anode material and acetylene black and Kynoar (PVDF) are processed anode pole piece according to 80: 10: 10 mass ratio.With the metal lithium sheet is negative pole, 1M LiPF
6/ (EC+DMC (volume ratio is 1: 1)) is organic system electrolyte, is assembled into button cell.This material under the charge-discharge magnification of 0.5C, 3C first discharge capacity be respectively 162mAh/g, 138mAh/g, 20 circulation volume conservation rates are respectively 92%, 82% between 2.5-4.3V.
Embodiment 2
(1) with 0.3 mole of NiO, 0.15 mole of Co
2O
3, 0.3 mole of MnO
2, 0.52 mole of Li
2CO
3With 0.1 mole of TiO
2Mix and add the 40mL deionized water and carry out ball milling, ball milling speed 200rpm, ball milling time 24h.Material behind the mixing 60 ℃ of oven dry, is warming up to 800 ℃ and be incubated 20h with the heating rate of 10 ℃/min again, naturally cools to room temperature and make Li (Ni
1/3Co
1/3Mn
1/3)
0.9Ti
0.1O
2Composite positive pole;
(2) with 1g Li (Ni
1/3Co
1/3Mn
1/3)
0.9Ti
0.1O
2Composite positive pole mixes with 0.1g SnO2, adds the 20mL deionized water and carries out ball milling, ball milling speed 400rpm, ball milling time 8h.After 70 ℃ of oven dry, the heating rate with 10 ℃/min is warming up to 700 ℃ again with the material behind the mixing, and insulation 4h naturally cools to room temperature and makes Li (Ni
1/3Co
1/3Mn
1/3)
0.9Ti
0.1O
2/ SnO
2Composite positive pole.This material under the charge-discharge magnification of 0.5C, 3C first discharge capacity be respectively 158mAh/g, 132mAh/g, 20 circulation volume conservation rates are respectively 90%, 81% between 2.5-4.3V.
Embodiment 3
(1) with 0.3 mole of Ni (NO
3)
2, 0.3 mole of Co (NO
3)
2, 0.3 mole of Mn (NO
3)
2, 1.05 moles of LiNO
3With 0.1 mole of MgCO
3Mix and add 40mL acetone and carry out ball milling, ball milling speed 500rpm, ball milling time 12h.Material behind the mixing 60 ℃ of oven dry, is warming up to 1000 ℃ and be incubated 5h with the heating rate of 8 ℃/min again, naturally cools to room temperature and make Li (Ni
1/3Co
1/3Mn
1/3)
0.9Mg
0.1O
2Composite positive pole;
(2) with 1g Li (Ni
1/3Co
1/3Mn
1/3)
0.9Mg
0.1O
2Composite positive pole and 0.1g SnO
2Mix, add 20mL acetone and carry out ball milling, ball milling speed 300rpm, ball milling time 10h.After 70 ℃ of oven dry, the heating rate with 10 ℃/min is warming up to 1000 ℃ again with the material behind the mixing, and insulation 4h naturally cools to room temperature and makes Li (Ni
1/3Co
1/3Mn
1/3)
0.9Mg
0.1O
2/ SnO
2Composite positive pole.This material under the charge-discharge magnification of 0.5C, 3C first discharge capacity be respectively 146mAh/g, 122mAh/g, 20 circulation volume conservation rates are respectively 88%, 78% between 2.5-4.3V.
Embodiment 4
(1) with 0.995 mole of Ni
1/3Co
1/3Mn
1/3(OH)
2, 0.52 mole of Li
2CO
3With 0.005 mole of Al (OH)
3Mix and add the 50mL absolute ethyl alcohol and carry out ball milling, ball milling speed 400rpm, ball milling time 20h.Material behind the mixing 70 ℃ of oven dry, is warming up to 1050 ℃ and be incubated 20h with the heating rate of 6 ℃/min again, naturally cools to room temperature and make Li (Ni
1/3Co
1/3Mn
1/3)
0.995Al
0.05O
2Composite positive pole;
(2) with 1g Li (Ni
1/3Co
1/3Mn
1/3)
0.995Al
0.05O
2Composite positive pole and 0.08g SnO
2Mix, add the 10mL absolute ethyl alcohol and carry out ball milling, ball milling speed 400rpm, ball milling time 12h.After 70 ℃ of oven dry, the heating rate with 6 ℃/min is warming up to 850 ℃ again with the material behind the mixing, and insulation 5h naturally cools to room temperature and makes Li (Ni
1/3Co
1/3Mn
1/3)
0.995Al
0.05O
2/ SnO
2Composite positive pole.This material under the charge-discharge magnification of 0.5C, 3C first discharge capacity be respectively 148mAh/g, 126mAh/g, 20 circulation volume conservation rates are respectively 90%, 81% between 2.5-4.3V.
Embodiment 5
(1) with 0.95 mole of Ni
1/3Co
1/3Mn
1/3(NO
3)
2, 1.05 moles of LiOHH
2O and 0.05 mole of Cu (OH)
2Mix and add the anhydrous propyl alcohol of 60mL and carry out ball milling, ball milling speed 400rpm, ball milling time 18h.Material behind the mixing 70 ℃ of oven dry, is warming up to 950 ℃ and be incubated 20h with the heating rate of 6 ℃/min again, naturally cools to room temperature and make Li (Ni
1/3Co
1/3Mn
1/3)
0.95Cu
0.05O
2Composite positive pole;
(2) with 1g Li (Ni
1/3Co
1/3Mn
1/3)
0.95Cu
0.05O
2Composite positive pole and 0.06g SnO
2Mix, add the anhydrous propyl alcohol of 10mL and carry out ball milling, ball milling speed 500rpm, ball milling time 12h.After 70 ℃ of oven dry, the heating rate with 6 ℃/min is warming up to 900 ℃ again with the material behind the mixing, and insulation 5h naturally cools to room temperature and makes Li (Ni
1/3Co
1/3Mn
1/3)
0.95Cu
0.05O
2/ SnO
2Composite positive pole.This material under the charge-discharge magnification of 0.5C, 3C first discharge capacity be respectively 152mAh/g, 130mAh/g, 20 circulation volume conservation rates are respectively 93%, 82% between 2.5-4.3V.
Embodiment 6
(1) with 0.25 mole of NiSO
4, 0.2 mole of CoSO
4, 0.4 mole of MnSO
4, 0.52 mole of Li
2SO
4With 0.15 mole of Cr (NO
3)
39H
2O mixes and adds 60mL acetone and carries out ball milling, ball milling speed 100rpm, ball milling time 36h.Material behind the mixing 40 ℃ of oven dry, is warming up to 500 ℃ and be incubated 25h with the heating rate of 2 ℃/min again, naturally cools to room temperature and make LiNi
0.25Co
0.2Mn
0.4Cr
0.15O
2Composite positive pole;
(2) with 0.99g LiNi
0.25Co
0.2Mn
0.4Cr
0.15O
2Composite positive pole and 0.01gSnSO
4Mix, add 10mL acetone and carry out ball milling, ball milling speed 100rpm, ball milling time 36h.After 40 ℃ of oven dry, the heating rate with 2 ℃/min is warming up to 600 ℃ again with the material behind the mixing, and insulation 10h naturally cools to room temperature and makes LiNi
0.25Co
0.2Mn
0.4Cr
0.15O
2/ SnO
2Composite positive pole.This material under the charge-discharge magnification of 0.5C, 3C first discharge capacity be respectively 147mAh/g, 125mAh/g, 20 circulation volume conservation rates are respectively 90%, 80% between 2.5-4.3V.
Embodiment 7
(1) with 0.7 mole of acetic acid nickel, 0.15 mole of acetic acid cobalt, 0.149 mole of acetic acid manganese, 1.05 mole of acetic acid lithiums and 0.001 mole of Si (CO
3)
2Mix and add the 60mL cyclopentanone and carry out ball milling, ball milling speed 500rpm, ball milling time 8h.Material behind the mixing 120 ℃ of oven dry, is warming up to 1200 ℃ and be incubated 3h with the heating rate of 12 ℃/min again, naturally cools to room temperature and make LiNi
0.7Co
0.15Mn
0.149Si
0.001O
2Composite positive pole;
(2) with 0.75g LiNi
0.7Co
0.15Mn
0.149Si
0.001O
2Composite positive pole mixes with the 0.25g stannous oxalate, adds the 10mL cyclopentanone and carries out ball milling, ball milling speed 300rpm, ball milling time 6h.After 120 ℃ of oven dry, the heating rate with 10 ℃/min is warming up to 1300 ℃ again with the material behind the mixing, and insulation 2h naturally cools to room temperature and makes LiNi
0.7Co
0.15Mn
0.149Si
0.001O
2/ SnO
2Composite positive pole.This material under the charge-discharge magnification of 0.5C, 3C first discharge capacity be respectively 146mAh/g, 129mAh/g, 20 circulation volume conservation rates are respectively 91%, 80% between 2.5-4.3V.
Embodiment 8
(1) 0.1 mole of nickel oxalate, 0.5 mole of cobalt oxalate, 0.2 mole of manganese oxalate, 0.56 mole of lithium oxalate and 0.1 mole of lanthanum oxalate are mixed and add the 60mL amylalcohol and carry out ball milling, ball milling speed 500rpm, ball milling time 8h.Material behind the mixing 100 ℃ of oven dry, is warming up to 1300 ℃ and be incubated 3h with the heating rate of 7 ℃/min again, naturally cools to room temperature and make LiNi
0.1Co
0.5Mn
0.2La
0.2O
2Composite positive pole;
(2) with 0.8g LiNi
0.1Co
0.5Mn
0.2La
0.2O
2Composite positive pole mixes with the 0.2g stannous oxalate, adds the 10mL amylalcohol and carries out ball milling, ball milling speed 500rpm, ball milling time 7h.After 100 ℃ of oven dry, the heating rate with 5 ℃/min is warming up to 500 ℃ again with the material behind the mixing, and insulation 26h naturally cools to room temperature and makes LiNi
0.1Co
0.5Mn
0.2La
0.2O
2/ SnO
2Composite positive pole.This material under the charge-discharge magnification of 0.5C, 3C first discharge capacity be respectively 145mAh/g, 127mAh/g, 20 circulation volume conservation rates are respectively 90%, 78% between 2.5-4.3V.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the lithium nickel cobalt manganese oxygen of a doped metallic elements/tin oxide composite positive pole is characterized in that, said lithium nickel cobalt manganese oxygen/tin oxide chemical expression is: LiNi
xCo
yMn
zR
zO
2/ SnO
2, wherein, 0.1≤x≤0.7,0.1≤y≤0.7,0.1≤z≤0.7,0.001≤z '≤0.2, said x+y+z+z '=1.
2. composite positive pole according to claim 1 is characterized in that preferred 0.15≤x≤0.6,0.15≤y≤0.6,0.15≤z≤0.6,0.005≤z '≤0.15, said x+y+z+z '=1;
Further preferred, 0.15≤x≤0.5,0.15≤y≤0.5,0.15≤z≤0.5,0.005≤z '≤0.15, said x+y+z+z '=1;
Preferred especially, 0.2≤x≤0.4,0.2≤y≤0.4,0.2≤z≤0.4,0.005≤z '≤0.1, said x+y+z+z '=1.
3. composite positive pole according to claim 1 or claim 2; It is characterized in that; Said doped metallic elements is any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, vanadium, barium, germanium, indium, tantalum, tin or the rare earth element; Be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, vanadium, barium, the tin; Further be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, the tin, be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, the chromium especially.
4. the preparation method of the lithium nickel cobalt manganese oxygen like one of claim 1-3 said doped metallic elements/tin oxide composite positive pole may further comprise the steps:
(1) with the compound of nickel, cobalt, manganese, lithium salts and doping metals compound mix, and again the mixture that obtains are carried out high temperature solid state reaction, obtain the lithium nickel cobalt manganese oxygen composite positive pole of doped metallic elements;
Carry out high temperature solid state reaction again after the lithium nickel cobalt manganese oxygen composite positive pole of the doped metallic elements that (2) step (1) is obtained and tin metal compound mix, obtain the lithium nickel cobalt manganese oxygen/tin oxide composite positive pole of doped metallic elements.
5. like the said method of claim 4, it is characterized in that, said method comprising the steps of:
(1) with the compound of nickel, cobalt, manganese; Lithium salts and doping metals compound with the dry materials behind the mixing, are warming up to 500 ℃～1300 ℃ and be incubated and carry out high temperature solid state reaction more than the 3h; Cool off, make the lithium nickel cobalt manganese oxygen composite positive pole of doped metallic elements;
(2) with the lithium nickel cobalt manganese oxygen composite positive pole and the 1wt%～25wt% tin metal compound of 75wt%～99wt% doped metallic elements; Behind the dry materials behind the mixing; Be warming up to 500 ℃～1300 ℃; Carry out high temperature solid state reaction more than the insulation 2h, cool off, make the lithium nickel cobalt manganese oxygen/tin oxide composite positive pole of doped metallic elements.
6. like claim 4 or 5 said methods, it is characterized in that the dry ball milling that preferably carries out before after mixing described in the step (1);
Preferably, ball milling described in the step (1) is specially and adds the mix grinding medium and carry out ball milling;
Preferably, ball milling speed is more than the 100rpm described in the step (1), further is preferably more than the 200rpm, is preferably 200rpm～500rpm especially; The preferred said ball milling time is more than the 8h, further is preferably more than the 12h, is preferably 12h～24h especially;
Preferably, in the step (1), the solid content of the mixture of said adding mix grinding medium is 50%～90%, is preferably 60%～80% especially;
Preferably, in the step (1), said drying further is preferably 40 ℃～120 ℃ oven dry for oven dry, more preferably 40 ℃～100 ℃ oven dry, is preferably especially 60 ℃～70 ℃ oven dry.
7. like each said method of claim 4-6, it is characterized in that, in the step (1), said heating rate be preferably 2 ℃/more than the min, further be preferably 5 ℃/more than the min, be preferably 5 ℃/min～10 ℃/min especially;
Preferably, in the step (1), said high temperature solid state reaction temperature is 600 ℃～1200 ℃, more preferably 700 ℃～1100 ℃, is preferably 800 ℃～1050 ℃ especially;
Preferably, in the step (1), the said high temperature solid state reaction time is more than the 5h, further is preferably 5h～25h, is preferably 5h～20h especially;
Preferably, in the step (1), the said natural cooling that is cooled to further is preferably and naturally cools to room temperature;
Preferably, in the step (1), in the lithium nickel cobalt manganese oxygen composite positive pole of said doped metallic elements, the molal quantity of lithium approximates doped metallic elements, nickel, cobalt, manganese total mole number.
8. like each said method of claim 4-7; It is characterized in that; In the step (2); The addition of the lithium nickel cobalt manganese oxygen composite positive pole of doped metallic elements is preferably the 80wt%～99wt% of the mixture gross mass that obtains, and further is preferably 85wt%～97wt%, is preferably 90wt%～95wt% especially; The addition of tin metal compound is preferably the 1wt%～20wt% of the mixture gross mass that obtains, and further is preferably 3wt%～15wt%, is preferably 5wt%～10wt% especially;
Preferably, mix the dry afterwards ball milling that carries out before described in the step (2);
Preferably, ball milling described in the step (2) is specially and adds the mix grinding medium and carry out ball milling;
Preferably, the solid content that adds the mixture of mix grinding medium described in the step (2) is 70%～95%, is preferably 80%～90% especially;
Preferably, in the step (2), said ball milling speed is more than the 100rpm, further is preferably more than the 200rpm, is preferably 200rpm～400rpm especially; The preferred spheres time consuming further is preferably more than the 6h for more than the 4h, more preferably more than the 8h, is preferably 8h～16h especially;
Preferably, in the step (2), said drying further is preferably 40 ℃～120 ℃ oven dry for oven dry, more preferably 40 ℃～100 ℃ oven dry, is preferably especially 60 ℃～70 ℃ oven dry.
9. like each said method of claim 4-8, it is characterized in that, in the step (2), heating rate be preferably 2 ℃/more than the min, further be preferably 5 ℃/more than the min, be preferably 5 ℃/min～10 ℃/min especially;
Preferably, in the step (2), the high temperature solid state reaction temperature is 500 ℃～1200 ℃, further is preferably 600 ℃～1100 ℃, is preferably 700 ℃～1000 ℃ especially;
Preferably, in the step (2), the high temperature solid state reaction time is more than the 3h, further is preferably 4h～10h, is preferably 4h～6h especially;
Preferably, in the step (2), the said natural cooling that is cooled to further is preferably and naturally cools to room temperature.
10. like each said method of claim 4-9, it is characterized in that preferred said mix grinding medium is water, C
1-C
10Alcohol, C
3-C
10Ketone or its mixture, further be preferably water, C
1-C
5Alcohol, C
3-C
5Ketone or its mixture, be preferably deionized water, ethanol and acetone or its mixture especially;
The compound of preferred said nickel, cobalt, manganese comprises nitrate, carbonate, acetate, citrate, sulfate, oxalates, formates or nickel, cobalt, manganese hydroxide and nickel, the cobalt of nickel, cobalt, manganese, in the Mn oxide one or more, and further the compound of preferred said nickel, cobalt, manganese comprises one or more in nitrate, carbonate, acetate, citrate, sulfate or the nickel of nickel, cobalt, manganese, cobalt, manganese hydroxide and nickel, cobalt, the Mn oxide;
Preferred said lithium salts comprises one or more in nitrate, carbonate, acetate, citrate, sulfate, oxalates, formates or the lithium hydroxide of lithium, and further preferred said lithium salts comprises one or more in nitrate, carbonate, acetate, citrate, sulfate or the lithium hydroxide of lithium;
Preferred said doping metals compound comprises nitrate, carbonate, acetate, citrate, sulfate, oxalates, formates or the doping metals hydroxide of doping metals, in the blended metal oxide one or more, and further preferred said doping metals compound comprises nitrate, carbonate, acetate, citrate, sulfate or the doping metals hydroxide of doping metals, in the blended metal oxide one or more;
Preferred said doped metallic elements is any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, vanadium, barium, germanium, indium, tantalum, tin or the rare earth element; Be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, vanadium, barium, the tin; Further be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, chromium, lanthanum, molybdenum, strontium, tungsten, the tin, be preferably any or its combination in titanium, aluminium, magnesium, copper, zirconium, silicon, the chromium especially;
Preferred especially said blended metal oxide comprises one or more in titanium dioxide, aluminium oxide, magnesia, cupric oxide, zirconia, silica, the chromium oxide;
Preferred said tin metal compound comprises one or more in nitrate, carbonate, acetate, citrate, sulfate, oxalates, formates or the tin oxide of tin, and further preferred said tin metal compound comprises one or more in nitrate, carbonate, acetate, citrate, sulfate or the tin oxide of tin.
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