CN100342569C - Method for synthesizing lithium ion cell positive cell polar material rotary furnace - Google Patents
Method for synthesizing lithium ion cell positive cell polar material rotary furnace Download PDFInfo
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- CN100342569C CN100342569C CNB2005100359496A CN200510035949A CN100342569C CN 100342569 C CN100342569 C CN 100342569C CN B2005100359496 A CNB2005100359496 A CN B2005100359496A CN 200510035949 A CN200510035949 A CN 200510035949A CN 100342569 C CN100342569 C CN 100342569C
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Abstract
The present invention relates to a method using a rotary furnace for calcining and synthesizing an anode material of lithium ion cells, which comprises the following steps: step 1, the lithic hydroxide, oxide or salt is mixed with the hydroxide, oxide or salt of transition metal to be moved into a rotary furnace; step 2, the temperature in the rotary furnace is controlled at 600 to 950 DEG C, the rotational speed is controlled at 2 to 5 revolutions per minute, and after being calcined for 20 to 40 hours in the rotary furnace, the mixture is cooled; step 3, the cooled material is pulverized and sieved to obtain the product of the anode material of lithium ion cells. The present invention uses the rotary furnace for calcination, and the calcined material is uniformly heated. Thus, the uniformity of the physical performance and the chemical property of the calcined material is improved. Because the heating of the rotary furnace is uniform, the time of high-temperature treatment can be correspondingly shortened, and the energy consumption can be obviously reduced.
Description
Technical field
The invention belongs to battery technology, particularly a kind of method of synthesizing lithium ion cell positive cell polar material rotary furnace.
Background technology
The building-up process of the lithium of anode material for lithium-ion batteries such as cobalt acid at present, LiMn2O4, lithium nickelate, LiFePO 4, lithium vanadate etc. all need be passed through the high-temperature calcination step, and the equipment that this step adopted is traditional high temperature furnace usually, as Muffle furnace, tunnel kiln.Concrete operations are that lithium salts and other slaine are mixed according to a certain percentage, in the resistant to elevated temperatures container (as crucible) of packing into, place calcining a period of time in the high temperature furnace.Lithium salts commonly used has lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate etc., and other then is salt or corresponding oxide, and calcining heat is 600～1000 ℃ even higher temperature, and calcination time is about 20～60h.The method technology of this synthesizing lithium ion cell positive cell polar material is simple, easily extensive industrialization, but also there is significant disadvantages:
(1) product lack of homogeneity
What the mode of heating of conventional high-temperature stove adopted is static calcining pattern.Its heating source generally is fixed on body of heater inside, for different splendid attire container of material, be subjected to the restriction of high temperature furnace self accuracy of manufacture and temperature-controlled precision, the situation of being heated of diverse location can not be consistent in the same humidity province of the container of each splendid attire material in high temperature furnace; For same container, because the material in the container remains static, the situation of being heated that is in peripheral position and center, position, top layer and interior location material also is difficult to consistent, so can cause inhomogeneous on positive electrode physics after the calcining, the chemical property.
(2) heat efficiency is low, and energy waste is big
For the material that guarantees diverse location in material in the different vessels and the same container is heated evenly and fully, just must prolong the high-temperature process time, so energy consumption is bigger.
In addition, conventional high-temperature stove such as Muffle furnace, tunnel kiln oven body part closure are poor, and the thermal loss that causes by heat radiation is bigger, so the heat efficiency is low, energy waste is big.
(3) the easily-consumed products consumption is big, the production cost height
Break easily even damage fully after the container of splendid attire material (as crucible) is calcined through multiple high temp, need constantly to change, cause production cost to increase.
(4) the material waste is many, pollutes big
During large-scale production, the forward and backward needs of high-temperature process constantly move into material a large amount of high-temperature resistant container (as crucible) and take out from these containers, and the material waste that this transfer process causes is many, and dust pollution is also big simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of method of synthesizing lithium ion cell positive cell polar material rotary furnace, overcome the shortcoming of the method existence of present high-temperature calcination synthesis of anode material of lithium-ion battery.
The method of synthesizing lithium ion cell positive cell polar material rotary furnace of the present invention may further comprise the steps:
(1) hydroxide of lithium, oxide or salt mix with hydroxide, oxide or the salt of transition metal, move in the rotary furnace;
(2) temperature in the rotary furnace is controlled at 600～950 ℃, rotating speed is controlled at 2～5 rev/mins, and mixture is calcined cooling after 20～40 hours in rotary furnace;
(3) cooled material through pulverize, sieve the anode material for lithium-ion batteries product.
Described in the step (1) the transition metal optimal selection be in cobalt, nickel, manganese, iron, the vanadium one or more.
The salt optimal selection of the transition metal described in the step (1) is one or more in nitrate, carbonate, phosphate, oxalates, the acetate.
In order to satisfy the various performance demands of battery, can mix in hydroxide, oxide or the salt of boron, magnesium, aluminium, cobalt, nickel, manganese, vanadium, chromium, calcium, yttrium, thulium, gadolinium, holmium, lanthanum, neodymium one or more in the mixture of hydroxide, oxide or the salt of the lithium described in the step (1) and hydroxide, oxide or the salt of transition metal.
The hydroxide of the hydroxide of described lithium, oxide or salt and transition metal, oxide or salt, and the mol ratio of hydroxide, oxide or the salt of the boron that mixes, magnesium, aluminium, cobalt, nickel, manganese, vanadium, chromium, calcium, yttrium, thulium, gadolinium, holmium, lanthanum, neodymium, fluorine, phosphorus is: the molar fraction of 1～1.1 * lithium in target end-product chemical formula: transition metal in target end-product chemical formula molar fraction: doping element in target end-product chemical formula molar fraction; That is:
If the chemical formula of target end-product is LiM
xA
yB
zO
n, in the formula, described M is cobalt, nickel, manganese, iron or vanadium; A, B are respectively boron, magnesium, aluminium, cobalt, nickel, manganese, vanadium, chromium, calcium, yttrium, thulium, gadolinium, holmium, lanthanum, neodymium; X, y, z, n are respectively M, A, B, the molar fraction of O element in the target end-product, 0≤y+z≤x, then
The hydroxide of the hydroxide of described lithium, oxide or salt and transition metal, oxide or salt, and the mol ratio of hydroxide, oxide or the salt of the boron that mixes, magnesium, aluminium, cobalt, nickel, manganese, vanadium, chromium, calcium, yttrium, thulium, gadolinium, holmium, lanthanum, neodymium, fluorine, phosphorus is 1～1.1: x: y: z.
Can feed the gas of accelerating oxidation or prevention oxidation in the rotary furnace described in the step (2) as required.
Described gas is one or more in nitrogen, argon gas, oxygen, air, the hydrogen.
The present invention both can be used for preparing anode material for lithium-ion batteries such as the cobalt acid lithium, LiMn2O4, lithium nickelate, nickel cobalt manganese lithium, LiFePO 4, lithium vanadate of non-impurity-doped element, also can be used to prepare anode material for lithium-ion batteries such as the cobalt acid lithium that contains doped chemical, LiMn2O4, lithium nickelate, nickel cobalt manganese lithium, LiFePO 4, lithium vanadate.
The present invention compared with prior art has following advantage:
(1) good product consistency
Because what the mode of heating of rotary furnace adopted is rotation dynamic calcining pattern, by the material calcined along with burner hearth constantly stirs around the continuous rotation of body of heater central axis, mixing effect is good, being heated evenly of material in this process, therefore the physics of calcining back material, the homogeneity of chemical property also increase.
(2) heat efficiency height, energy-saving effect is obvious
Because the rotary furnace homogeneous heating, the high-temperature process time can correspondingly shorten, and can obviously cut down the consumption of energy;
In addition, the oven body part closure of rotary furnace is good, and the thermal loss that causes by heat radiation is little, so heat efficiency height, energy savings.
(3) easily-consumed products are few, and production cost is low
When adopting the rotary furnace calcining, material moves in the burner hearth by feed arrangement, and the material after calcining is finished is removed by drawing mechanism, does not need resistant to elevated temperatures container (as crucible), therefore can reduce production costs.
(4) waste of material reduces, environmental protection more
Because adopt the rotary furnace calcining to compare with traditional high-temperature calcination, input and output material is convenient, has simplified production technology, the material waste reduces the also corresponding minimizing of dust pollution.
Description of drawings
Fig. 1 is the structural representation of the rotary furnace that adopts of the present invention;
Among the figure: 1-feed arrangement, 2-rotary furnace body of heater, 3-heating jacket, 4-inlet duct, 5-exhaust apparatus, 6-drawing mechanism.
Embodiment
As shown in Figure 1, operation principle of the present invention is: the form of this rotary furnace heats in heating jacket 3 for the body of heater 2 of rotation, material moves in the rotary furnace body of heater 2 by feed arrangement 1, material is along with the rotation of rotary furnace body of heater 2 is moved to an end of drawing mechanism 6 gradually then, and carries out high-temperature calcination in this process.Can be by inlet duct 4 to body of heater 2 internal feed desired gas, exhaust apparatus 5 can be discharged the gas in the body of heater 2.Material after calcining is finished finally is moved out of the rotary furnace body of heater by drawing mechanism 6.
Embodiment 1:
Lithium ion cell anode material lithium cobaltate (LiCoO
2) preparation: with raw material Co
3O
4With LiOHH
2O is Li in molar ratio: Co=1.02: 1 evenly mixes, and moves into then in the rotary furnace, and temperature is 800 ℃ in the rotary furnace, 2 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets cobalt acid lithium product after pulverizing, sieving.The uniform particles of this product, the electrochemical reversible capacity reaches more than the 135mAh/g, and cycle performance is good.
Embodiment 2:
Anode material for lithium-ion batteries LiCo
0.5Mn
0.5O
2Preparation: with raw material CH
3COOLi and (CH
3COO)
3Co is Li in molar ratio: Co=1.03: in the 0.5 water-soluble solution, add glycolic (HOCH
2CO
2H), stirring condition slowly adds ammoniacal liquor down and regulates pH=6.5～7, adds LiMn after the evaporation and concentration
2O
4, add LiMn
2O
4The mol ratio of each material of back is Li: Co: Mn=1.03: 0.5: 0.5, continue to stir, and filtration, drying move in the rotary furnace then, and temperature is 800 ℃ in the rotary furnace, 3 rev/mins of rotating speeds, material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.5Mn
0.5O
2Product.The uniform particles of this product, the electrochemical reversible capacity reaches more than the 120mAh/g, and cycle performance is good, and high-temperature behavior is good.
Embodiment 3:
Anode material for lithium-ion batteries LiCo
0.5Ni
0.5O
2Preparation: with LiOHH
2O, Co
3O
4, Ni (OH)
2Be raw material, in molar ratio Li: Ni: Co=1: evenly mix at 0.5: 0.5, move into then in the rotary furnace, temperature is 670 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 40h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.5Ni
0.5O
2Product.Its electrochemical reversible capacity is 170mAh/g, and cycle performance is good.
Embodiment 4:
Anode material for lithium-ion batteries LiCo
0.9Al
0.1O
2Preparation: with raw material Li NO
3With Co
3O
4, Al (NO
3)
3Li: Co: Al=1.05 in molar ratio: evenly mix at 0.9: 0.1, move into then in the rotary furnace, temperature is 900 ℃ in the rotary furnace, 2 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.9Al
0.1O
2Product.Its electrochemical reversible capacity reaches more than the 130mAh/g, and cycle performance is good.
Embodiment 5:
Anode material for lithium-ion batteries LiCo
0.95Mg
0.05O
2Preparation: with raw material Li NO
3With Co
3O
4, Mg (NO
3)
2Li: Co: Mg=1.03 in molar ratio: evenly mix at 0.95: 0.05, move into then in the rotary furnace, temperature is 800 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 40h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.95Mg
0.05O
2Product.The uniform particles of this product, the electrochemical reversible capacity reaches more than the 135mAh/g, and cycle performance is good.
Embodiment 6:
Anode material for lithium-ion batteries LiCo
0.85B
0.15O
2Preparation: with raw material Li OH and Co
3O
4, LiBO
2Li: Co: B=1.02 in molar ratio: evenly mix at 0.85: 0.15, move into then in the rotary furnace, temperature is 800 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 40h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.85B
0.15O
2Product.Its electrochemical reversible capacity reaches more than the 125mAh/g, and cycle performance is good.
Embodiment 7:
Anode material for lithium-ion batteries LiCo
0.9Ca
0.1O
2Preparation: with raw material Li NO
3With Co
3O
4, Ca (NO
3)
2Li: Co: Ca=1.02 in molar ratio: evenly mix at 0.9: 0.1, move into then in the rotary furnace, temperature is 800 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 20h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.9Ca
0.1O
2Product.Its uniform particles, the electrochemical reversible capacity reaches more than the 140mAh/g, and cycle performance is good.
Embodiment 8:
Anode material for lithium-ion batteries LiCo
0.99Y
0.01O
2Preparation: with raw material Li NO
3With Co
3O
4, Y
2O
3Li: Co: Y=1.03 in molar ratio: evenly mix at 0.99: 0.01, move into then in the rotary furnace, temperature is 800 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.99Y
0.01O
2Product.Its electrochemical reversible capacity reaches more than the 140mAh/g, and cycle performance is good.
Embodiment 9:
Anode material for lithium-ion batteries LiCo
0.99La
0.01O
2Preparation: with raw material Li NO
3With Co
3O
4, La
2O
3Li: Co: La=1.03 in molar ratio: evenly mix at 0.99: 0.01, move into then in the rotary furnace, temperature is 800 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.99La
0.01O
2Product.Its particle diameter is even, and the electrochemical reversible capacity reaches more than the 140mAh/g, and cycle performance is good.
Embodiment 10:
Anode material for lithium-ion batteries LiCo
0.99Tm
0.01O
2Preparation: with raw material Li NO
3With Co
3O
4, Tm
2O
3Li: Co: Tm=1.03 in molar ratio: evenly mix at 0.99: 0.01, move into then in the rotary furnace, temperature is 800 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.99Tm
0.01O
2Product.Its electrochemical reversible capacity reaches more than the 140mAh/g, and cycle performance is good.
Embodiment 11:
Anode material for lithium-ion batteries LiCo
0.99Gd
0.01O
2Preparation: with raw material Li NO
3With Co
3O
4, Gd
2O
3Li: Co: Gd=1.03 in molar ratio: evenly mix at 0.99: 0.01, move into then in the rotary furnace, temperature is 800 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.99Gd
0.01O
2Product.Its electrochemical reversible capacity reaches more than the 140mAh/g, and cycle performance is good.
Embodiment 12:
Anode material for lithium-ion batteries LiCo
0.99Ho
0.01O
2Preparation: with raw material Li NO
3With Co
3O
4, Ho
2O
3Li: Co: Ho=1.02 in molar ratio: evenly mix at 0.99: 0.01, move into then in the rotary furnace, temperature is 800 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets LiCo after pulverizing, sieving
0.99Ho
0.01O
2Product.Its electrochemical reversible capacity reaches more than the 140mAh/g, and cycle performance is good.
Embodiment 13:
Lithium cell anode material lithium manganate (LiMn
2O
4) preparation: with LiOHH
2O and MnO
2Be raw material, in molar ratio Li: Mn=1.02: 2 evenly mix, and move into then in the rotary furnace, and temperature is 750 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 40h in rotary furnace, and take out the cooling back.Product promptly gets the LiMn2O4 product after pulverizing, sieving.Its uniform particles, the electrochemical reversible capacity can reach 120mAh/g, and cycle performance is good under the normal temperature.
Embodiment 14:
Anode material for lithium-ion batteries LiAl
0.1Mn
1.9O
4Preparation: with Li
2CO
3, MnO
2, Al (OH)
3Be raw material, in molar ratio Li: Al: Mn=1.1: evenly mix at 0.1: 2, move into then in the rotary furnace, temperature is 950 ℃ in the rotary furnace, 3.5 rev/mins of rotating speeds, and material is calcined 40h in rotary furnace, and take out the cooling back.Product promptly gets LiAl after pulverizing, sieving
0.1Mn
1.9O
4Product.Its electrochemical reversible capacity is 110mAh/g, and high temperature (55 ℃) performance and cycle performance are good.
Embodiment 15:
Anode material for lithium-ion batteries LiCr
0.4Mn
1.6O
4Preparation: with LiOHH
2O, Cr
2O
3, MnO
2Be raw material, in molar ratio Li: Cr: Mn=1.02: evenly mix at 0.4: 1.6, move into then in the rotary furnace, temperature is 750 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 40h in rotary furnace, and take out the cooling back.Product promptly gets LiCr after pulverizing, sieving
0.4Mn
1.6O
4Product.Its electrochemical reversible capacity is 115mAh/g, and high-temperature behavior and cycle performance are good.
Embodiment 16:
Anode material for lithium-ion batteries LiV
0.05Mn
1.95O
4Preparation: with lithium carbonate, V
2O
5, MnO
2Be raw material, in molar ratio Li: V: Mn=1.02: evenly mix at 0.05: 1.95, move into then in the rotary furnace, temperature is 800 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets LiV after pulverizing, sieving
0.05Mn
1.95O
4Product.LiV
0.05Mn
1.95O
4The uniform particles of product, electrochemical reversible capacity are 110mAh/g, and high-temperature behavior and cycle performance are good.
Embodiment 17:
Anode material for lithium-ion batteries LiNd
0.01Mn
1.99The preparation of O4: with LiOHH
2O, Nd
2O
3, MnO
2Be raw material, in molar ratio Li: Nd: Mn=1.02: evenly mix at 0.01: 1.99, move into then in the rotary furnace, temperature is 700 ℃ in the rotary furnace, 2 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets LiNd after pulverizing, sieving
0.01Mn
1.99O
4Product.Its electrochemical reversible capacity is 115mAh/g, and cycle performance is good.
Embodiment 18:
Lithium ion battery anode material nickel acid lithium (LiNiO
2) preparation: with LiNO
3, Ni (OH)
2Be raw material, in molar ratio Li: Ni=1.03: 1 evenly mixes, and moves into then in the rotary furnace, and temperature is 680 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 40h under the oxygen atmosphere condition, and take out the cooling back.Product promptly gets the lithium nickelate product after pulverizing, sieving.Its electrochemical reversible capacity is 180mAh/g, and cycle performance is good.
Embodiment 19:
Anode material for lithium-ion batteries LiMg
0.05Ni
0.95O
2Preparation: with LiNO
3, Ni (OH)
2, Mg (OH)
2Be raw material, in molar ratio Li: Mg: Ni=1: evenly mix at 0.05: 0.95, move into then in the rotary furnace, temperature is 690 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 30h under the oxygen atmosphere condition in rotary furnace, and take out the cooling back.Product promptly gets LiMg after pulverizing, sieving
0.05Ni
0.95O
2Product.Its electrochemical reversible capacity is 175mAh/g, and cycle performance is good.
Embodiment 20:
Anode material for lithium-ion batteries LiNi
0.7Co
0.3Al
0.25O
2Preparation: with LiNO
3, Co
3O
4, NiO, Al (OH)
3Be raw material, in molar ratio Li: Ni: Co: Al=1: evenly mix at 0.7: 0.3: 0.25, move into then in the rotary furnace, temperature is 700 ℃ in the rotary furnace, 4 rev/mins of rotating speeds, and material is calcined 40h in rotary furnace, and take out the cooling back.Product promptly gets LiNi after pulverizing, sieving
0.7Co
0.3Al
0.25O
2Product.Its electrochemical reversible capacity is 190mAh/g, and cycle performance is good.
Embodiment 21:
Lithium ferrous phosphate as anode material of lithium ion battery (LiFePO
4) preparation: with LiOHH
2O, FeC
2O
42H
2O and (NH
4)
2HPO
4Be raw material, in molar ratio Li: Fe: P=1: under nitrogen protection evenly mix at 1: 1, move into then in the rotary furnace, temperature is 600 ℃ in the rotary furnace, 2.5 rev/mins of rotating speeds, and material is calcined 30h in the nitrogen atmosphere condition, and take out the cooling back.Product promptly gets the LiFePO 4 product after pulverizing, sieving.The particle of this product is tiny, even, and the electrochemical reversible capacity is 140mAh/g, and cycle performance is good.
Embodiment 22:
Anode material for lithium-ion batteries LiCr
0.01Fe
0.99PO
4Preparation: with LiOHH
2O, FeC
2O
42H
2O, (NH
4)
2HPO
4And chromic acetate is raw material, Li in molar ratio: Cr: Fe: P=1: under argon shield evenly mix, then move into rotary furnace at 0.01: 0.99: 1; temperature is 600 ℃ in the rotary furnace; 5 rev/mins of rotating speeds, material is calcined 20h under the argon gas atmosphere condition, and take out the cooling back.Product promptly gets LiCr after pulverizing, sieving
0.01Fe
0.99PO
4The positive electrode product.The particle of this product is tiny, even, and the electrochemical reversible capacity is 148mAh/g, and high-rate performance and cycle performance are good.
Embodiment 23:
Anode material for lithium-ion batteries lithium vanadate (LiV
3O
8) preparation: with Li
2CO
3And V
2O
5Be raw material, in molar ratio Li: V=1: 3 evenly mix, and move into then in the rotary furnace, and temperature is 600 ℃ in the rotary furnace, 5 rev/mins of rotating speeds, and material is calcined 50h under the mixed-gas atmosphere of nitrogen and hydrogen, and take out the cooling back.Product promptly gets the lithium vanadate product after pulverizing, sieving.Its electrochemical reversible capacity is 130mAh/g, and cycle performance is good.
Embodiment 24:
Lithium ion battery anode material nickel cobalt manganese lithium [Li (Ni
1/3Co
1/3Mn
1/3) O
2] preparation: with Co (NO
3)
26H
2O, Ni (NO
3)
26H
2O and (CH
3CO
2) 2Mn6H
2O is a raw material, with they Ni: Co: Mn=1 in molar ratio: be dissolved in distilled water at 1: 1.This solution is slowly splashed in the 50ml water of 60 ℃ of constant temperature, also quick stirring, simultaneously with NaOH (6mol/L) and NH
3The mixed solution of OH (6.5mol/L) also slowly splashes in this 50ml water, to keep the pH value=11-12 of solution.With the sedimentation and filtration that obtains, and use the distilled water washes clean, again 65 ℃ down baking 12h to its drying, then with itself and Li
2CO
3Li: Ni: Co: Mn=1 in molar ratio: mixing back at 1/3: 1/3: 1/3 moves into rotary furnace, and temperature is 700 ℃ in the rotary furnace, 4.5 rev/mins of rotating speeds, and material is calcined 30h in rotary furnace, and take out the cooling back.Product promptly gets nickel cobalt manganese lithium product after pulverizing, sieving.Its electrochemical reversible capacity is 160mAh/g, the cycle performance excellence.
Claims (3)
1, a kind of method of synthesizing lithium ion cell positive cell polar material rotary furnace is characterized in that may further comprise the steps:
(1) hydroxide of lithium, oxide or salt mix with hydroxide, oxide or the salt of transition metal, move in the rotary furnace;
(2) temperature in the rotary furnace is controlled at 600～950 ℃, rotating speed is controlled at 2～5 rev/mins, and mixture is calcined cooling after 20～40 hours in rotary furnace;
(3) cooled material through pulverize, sieve the anode material for lithium-ion batteries product;
In the step (1), described transition metal is one or more in cobalt, nickel, manganese, iron, the vanadium; The salt of described transition metal is one or more in nitrate, carbonate, phosphate, oxalates, the acetate; Mix in hydroxide, oxide or the salt of boron, magnesium, aluminium, cobalt, nickel, manganese, vanadium, chromium, calcium, yttrium, thulium, gadolinium, holmium, lanthanum, neodymium one or more in the mixture of the hydroxide of the hydroxide of described lithium, oxide or salt and transition metal, oxide or salt;
The hydroxide of the hydroxide of described lithium, oxide or salt and transition metal, oxide or salt, and the mol ratio of hydroxide, oxide or the salt of the boron that mixes, magnesium, aluminium, cobalt, nickel, manganese, vanadium, chromium, calcium, yttrium, thulium, gadolinium, holmium, lanthanum, neodymium, fluorine, phosphorus is: the molar fraction of 1～1.1 * lithium in target end-product chemical formula: transition metal in target end-product chemical formula molar fraction: doping element in target end-product chemical formula molar fraction; That is:
The chemical formula of target end-product is LiM
xA
yB
zO
n, in the formula, described M is cobalt, nickel, manganese, iron or vanadium; A, B are respectively boron, magnesium, aluminium, cobalt, nickel, manganese, vanadium, chromium, calcium, yttrium, thulium, gadolinium, holmium, lanthanum, neodymium; X, y, z, n are respectively M, A, B, the molar fraction of O element in the target end-product, 0≤y+z≤x, then
The hydroxide of the hydroxide of described lithium, oxide or salt and transition metal, oxide or salt, and the mol ratio of hydroxide, oxide or the salt of the boron that mixes, magnesium, aluminium, cobalt, nickel, manganese, vanadium, chromium, calcium, yttrium, thulium, gadolinium, holmium, lanthanum, neodymium, fluorine, phosphorus is 1～1.1: x: y: z.
2, the method for synthesizing lithium ion cell positive cell polar material rotary furnace according to claim 1 is characterized in that feeding in the rotary furnace described in the step (2) gas.
3, the method for synthesizing lithium ion cell positive cell polar material rotary furnace according to claim 2 is characterized in that the gas that feeds is one or more in nitrogen, argon gas, oxygen, air, the hydrogen.
Priority Applications (1)
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